CN114427657A - 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
CN114427657A
CN114427657A CN202210114509.3A CN202210114509A CN114427657A CN 114427657 A CN114427657 A CN 114427657A CN 202210114509 A CN202210114509 A CN 202210114509A CN 114427657 A CN114427657 A CN 114427657A
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hydrogen storage
capillary
hydrogen
capillary tube
tube
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Chinese (zh)
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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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Priority to CN202210114509.3A priority Critical patent/CN114427657A/en
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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 refueling 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

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 connected 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 in situ 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 lighter 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 goals have prompted improvements in the cylinder. First, H must be reduced2The transportation cost of (2). For example, the total capital and operating costs of tubular trailers account for a significant portion of the price of delivering hydrogen. Second, the functional requirements of the hydrogen energy system, such as weight and bulk density, must be met to adequately match a hydrogen fuel cell vehicle with an equivalent gasoline vehicle.
For many years, cylinders have been the most widely used technology for the storage of compressed hydrogen and gas. It provides a low weight and volume storage density. The alternative to steel cylinders includes liquid H2The hydrogen storage tank comprises a tank, a composite compressed hydrogen tank, a gas storage tank, an adsorbent, metal hydride and chemical hydride.
Composite compression H2Gas storage tanks are typically made of an aluminum or polymer lining, lined with a polymer/carbon fiber coating. They are designated as type III and type IV. They provide a gravimetric and volumetric storage density of 5 wt% and 26g/L, respectively. Because the cost of carbon fiber is relatively high, the price of the composite gas cylinder made of carbon fiber is much higher than that of a steel gas cylinder. Due to the wide application of carbon fibers in aerospace composites, mass production of carbon fibers cannot reduce their high cost.
Chemical hydrides are metal hydrogen compounds that generate hydrogen by irreversible reactions at the point of use. The waste reaction products need to be recovered at a central facility. They can provide very high gravimetric capacities (> 100% sodium borohydride). However, chemical hydrides are relatively expensive. Furthermore, H2Operability of the generatorAnd recycling the stream of reaction products is a major disadvantage.
The adsorbent operates by physical adsorption, H2The molecules bind weakly to the microporous surface. Considerable storage capacity can only be achieved at low temperatures approaching 77K. In adsorbent-based storage tanks, H2Stored both as adsorbates and in the gas phase. The gas phase cannot access the volume occupied by the adsorbent framework. Above a certain pressure, this repulsion of the adsorbent framework becomes too severe and the efficiency of adsorbent removal is higher.
In recent years, activated carbon has been the best adsorbent for low temperature adsorption. However, their performance has not led to commercialization, and the use of combustible adsorbents (such as activated carbon) at low temperatures presents a risk of potential accumulation with contaminating oxygen.
Glass microspheres have been proposed as miniature hydrogen storage vessels for many years. Glass microspheres are attractive because failure of one microsphere is not expected to affect safety and the amount of hydrogen released is small. Filling and release is accomplished by heating the microspheres at ambient temperature. When the permeability of hydrogen in the microspheres is small, the temperature range is 100-. However, to date, glass microsphere systems have been considered to be uncompetitive to alternative hydrogen storage technologies. For example, one project demonstrated weight and volume capacities of only 2.2 wt% and 4g/L, respectively, which are much lower than type III and type IV cylinders.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-pressure hydrogen storage method and a gas cylinder, wherein high-pressure hydrogen is stored by an integrated capillary bundle internally filled with MOF and COF materials in situ, one end of the capillary bundle is inflated, the other end of the capillary bundle is deflated, the structure is simple, the use is high-efficiency, the hydrogen can be repeatedly filled, the cost is low, and the high-pressure hydrogen is 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, and a metal organic framework adsorption material and a covalent organic compound adsorption material are sequentially synthesized in situ in each hydrogen storage capillary; and external compressed hydrogen is connected from one end of the capillary tube bundle, and the hydrogen is stored in each hydrogen storage capillary tube in the capillary tube bundle.
The method for in-situ synthesizing the metal organic framework adsorption material in the hydrogen storage capillary comprises the following steps:
s1-1, mixing zinc nitrate Zn (NO)3)2 6H2Dissolving 0 and 4, 4' -benzene-1, 3, 5-triacyl tribenzoic acid in N, N-diethylformamide 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 tiny crystals, and pouring out a 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;
and S1-4, putting the soaked crystal into a vacuum oven, and drying for 6-8 hours at 110-120 ℃ to obtain the metal organic framework adsorbing material distributed in the capillary.
The method for in-situ synthesizing the covalent organic compound adsorbing material in the hydrogen storage capillary comprises the following steps:
s2-1, uniformly mixing the mixed solution of mesitylene and dioxane with tetrakis (4-boraphenyl) methane to form a second solution;
s2-2, enabling the second solution to enter the hydrogen storage capillary tube through vacuumizing, reacting for 80-110 hours at 80-85 ℃ to obtain a 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, thus obtaining the covalent organic compound adsorbing material distributed in the capillary;
or, the method for in-situ synthesizing the covalent organic compound adsorbing material in the hydrogen storage capillary comprises the following steps:
s3-1, uniformly mixing the mixed solution of mesitylene and dioxane with tetra (4-phenyl borate) silane to form a second solution;
s3-2, enabling the second solution to enter the hydrogen storage capillary tube through vacuum pumping, reacting for 80-110 hours at 80-85 ℃ to obtain a white precipitate II, and pouring out the residual solution;
and S3-3, washing the obtained white precipitate II with anhydrous tetrahydrofuran, and then drying in vacuum at room temperature to remove the solvent, thereby obtaining the covalent organic compound adsorbing material distributed in the capillary.
Zinc nitrate Zn (NO) in the S1-13)2 6H20. The mass/volume ratio of 4, 4' -benzene-1, 3, 5-triacyl tribenzoic acid to N, N-diethylformamide is (17-20 mg) and (3.5-4.5 mg) is 1 mL;
the volume/mass ratio of trimethylbenzene, dioxane and tetra (4-boraphenyl) methane in the S2-1 is 1mL to 1mL (40-60 mg);
the volume/mass ratio of trimethylbenzene, dioxane and tetra (4-phenyl borate) silane in the S3-1 is 3mL to 1mL (50-60 mg).
A high-pressure hydrogen storage cylinder comprises a capillary tube bundle, a tube plate and an end cover, wherein the capillary tube bundle is used for storing hydrogen, the capillary tube bundle is composed of a plurality of hydrogen storage capillary tubes, a metal organic framework adsorption material and a covalent organic compound adsorption material are sequentially synthesized in situ in each hydrogen storage capillary tube, each hydrogen storage capillary tube in the capillary tube bundle vertically penetrates through the tube plate, two ends of each hydrogen storage capillary tube are provided with openings, and the end parts of the hydrogen storage capillary tubes are respectively flush with the end surfaces of the tube plate; the two end covers are respectively a first end cover provided with an air inlet and a second end cover provided with an air outlet, the open end of the first end cover is hermetically connected with the end face of the tube plate at one end of the capillary tube bundle, the open end of the second end cover is hermetically connected with the end face of the tube plate at the other end of the capillary tube bundle, and the 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 which vertically penetrate through the tube plate, and each hydrogen storage capillary in the capillary bundle correspondingly penetrates through each through hole.
The tube plate comprises a first tube plate and a second tube plate, the upper end surface of the first tube plate corresponds to the first end cover, the lower end surface of the second tube plate corresponds to the second end cover, and each hydrogen storage capillary on the capillary bundle respectively penetrates through the corresponding through hole on the first tube plate and the corresponding through hole on the second tube plate.
The tube sheet is outer along capillary tube bank length direction leads to long and is equipped with inner liner and outer shell, the inner liner will the tube sheet cladding, the outer shell sets up the inner liner outside, and extend to both ends end cover department, or will the end cover covers.
The air inlet of the first end cover is integrated with a first adapter used 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 used 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 in one of a round shape, a hexagon shape, a trapezoid shape, a rectangle shape, a triangle shape or an oval shape, the diameter or the cross section width of the hydrogen storage capillary tube is 0.1mm-8mm, and the number, the end surface 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 adsorption material or covalent organic compound adsorption material is 1nm-5 mu m.
The tube plate is a solid polymer tube plate; the lining 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 hydrogen stored 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 connected with the end cover through a complementary thread in a sealing mode.
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 sheet to its diameter or cross-sectional width is greater 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 in situ at the same time for hydrogen storage, has high hydrogen storage pressure (up to 150MPa), strong hydrogen storage capacity (the weight hydrogen storage density is up to 20-25 percent, and the volume hydrogen storage density is up to 70-80 g/L), low manufacturing cost, realizes the storage of high-pressure hydrogen in a relatively lighter container, and has higher commercial application value.
B. Compared with the conventional container with an opening at one end, the high-pressure hydrogen storage cylinder is simple to operate, avoids frequent opening and closing of ports when a single-port gas cylinder is charged and discharged, and is more convenient to use.
C. Compared with a high-pressure hydrogen storage tank, the capillary hydrogen storage technology is formed by combining numerous tiny pressure-resistant capillaries to form an ultra-strong stable structure. Each fine capillary tube is used as a single pressure container, and because the hydrogen storage capacity of the single capillary tube is extremely small, the hydrogen leakage cannot form an explosion environment.
D. The capillary tube hydrogen storage technology is convenient to connect and quick to charge hydrogen. The capillary hydrogen storage technology is a modular structure, and the shape, size and capacity of the hydrogen storage cylinders can be designed and installed at will to couple to any desired consumer system. For example, the fuel cell system can be mounted on a hydrogen fuel cell vehicle to supply power to the fuel cell.
Drawings
In order to more clearly illustrate the embodiments of the invention, the drawings that are required for the embodiments will be briefly described below, it being apparent that the drawings in the following description are some embodiments of the invention, and that other drawings may be derived from those drawings without inventive effort by a person skilled in the art.
FIG. 1 is a perspective view showing the overall construction of a high-pressure hydrogen storage cylinder provided in the present invention;
FIG. 2 is a schematic view of the bottle of FIG. 1;
fig. 3 is a schematic cross-sectional view of the capillary bundle structure of fig. 1.
The labels in the figure are 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 technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular 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 otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; the connection can be mechanical connection or electrical connection; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled 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 synthesized in each hydrogen storage capillary in situ in sequence; forming a plurality of hydrogen storage capillary tubes into a capillary tube bundle; and external compressed hydrogen is connected from one end of the capillary tube bundle, and the hydrogen is stored 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 that the 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 an MOF material, because the skeleton of the COF material is completely composed of light elements (H, B, O, C, Si and the like), the COF material has low crystal density and is more beneficial to the adsorption of hydrogen, and hydrogen elements are connected through strong covalent bonds (C-C, C-O, B-O, Si-C and the like), so that a one-dimensional or three-dimensional porous structure can be formed, the specific surface area is high, and the COF material is suitable for hydrogen storage. According to the structural characteristics of the capillary tube, the MOF and the COF are synthesized in situ in the capillary tube, and the particle diameters of the MOF and the COF are 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 in-situ synthesizing the metal organic framework adsorption material inside the capillary tube comprises the following steps:
s1-1, mixing zinc nitrate Zn (NO)3)2 6H2Dissolving 0 and 4,4 '-benzene-1, 3, 5-triacyl tribenzoic acid in N, N-diethylformamide to form a first solution, wherein the mass/volume ratio of the 0 and 4, 4' -benzene-1, 3, 5-triacyl tribenzoic acid to the N, N-diethylformamide is (17-20 mg): 3.5-4.5 mg):1 mL;
s1-2, enabling the first solution to enter the hydrogen storage capillary tube through vacuumizing, reacting for two days at 80-85 ℃ to generate tiny crystals, and pouring out a 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;
and S1-4, putting the soaked crystal into a vacuum oven, and drying for 6-8 hours at 110-120 ℃ to obtain the metal organic framework adsorbing material distributed in the capillary.
The method for in-situ synthesis of covalent organic compound adsorbing material in the capillary comprises the following steps:
s2-1, uniformly mixing a mixed solution of mesitylene and dioxane with 1mL (40-60 mg) of tetra (4-boratabhenyl) methane according to the volume/mass ratio of 1mL to form a second solution;
s2-2, enabling the second solution to enter the hydrogen storage capillary tube through vacuumizing, reacting for 80-110 hours at 80-85 ℃ to obtain a white precipitate I, and pouring out the residual solution;
and S2-3, washing the obtained white precipitate I with anhydrous tetrahydrofuran, and then drying in vacuum at room temperature to remove the solvent, thereby obtaining the covalent organic compound adsorbing material distributed in the capillary.
Alternatively, the method for in situ synthesis of covalent organic compound adsorbent material inside capillary is as follows:
s3-1, uniformly mixing the mixed solution of mesitylene and dioxane with 1mL (50-60 mg) of tetra (4-boraophenyl) silane in a volume/mass ratio of 3mL to 1mL to form a second solution;
s3-2, enabling the second solution to enter the hydrogen storage capillary tube through vacuum pumping, reacting for 80-110 hours at 80-85 ℃ to obtain a white precipitate II, and pouring out the residual solution;
and S3-3, washing the obtained white precipitate II with anhydrous tetrahydrofuran, and then drying in vacuum at room temperature to remove the solvent, thereby obtaining the covalent organic compound adsorbing material distributed in the capillary.
As shown in fig. 1-3, the present invention provides a high pressure hydrogen storage cylinder, which comprises a capillary tube bundle 1 for storing hydrogen, a tube sheet 2 and an end cover 5, wherein the capillary tube bundle 1 is composed 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, the tube sheet 2 is provided with a plurality of through holes 23 vertically penetrating through the tube sheet 2, each hydrogen storage capillary 11 in the capillary tube bundle 1 correspondingly and respectively penetrates through each through hole 23, two ends of the hydrogen storage capillary 11 are open, and the end parts are respectively flush with the end surface of the tube sheet 2. The number of the end covers 5 is two, and the end covers 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 open end of the first end cover 51 is hermetically connected with the end face of the tube plate 2 at one end of the capillary tube bundle 1, the open end of the second end cover 52 is hermetically connected 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 in situ at the same time for hydrogen storage, has high hydrogen storage pressure (up to 150MPa), strong hydrogen storage capacity (the weight hydrogen storage density is up to 16-18 percent, and the volume hydrogen storage density is up to 60-63 g/L), low manufacturing cost and realizes the storage of high-pressure hydrogen in a relatively light container. Compared with a high-pressure hydrogen storage tank, the capillary hydrogen storage technology is formed by combining numerous tiny pressure-resistant capillaries to form an ultra-strong stable structure. Each fine capillary tube is used as a single pressure container, and because the hydrogen storage capacity of the single capillary tube is extremely small, the hydrogen leakage cannot form an explosion environment.
Further, the tube sheet 2 includes a first tube sheet 21 and a second tube sheet 22, an upper end surface of the first tube sheet 21 corresponds to the first end cap 51, a lower end surface of the second tube sheet 22 corresponds to the second end cap 52, and each hydrogen storage capillary 11 on the capillary tube bundle 1 passes through the corresponding through hole 23 on the first tube sheet 21 and the second tube sheet 22, respectively. The tube sheet 2 is equipped with inner liner 3 and shell layer 4 along 1 length direction of capillary bank outward, and inner liner 3 sets up the cladding of tube sheet 2, and shell layer 4 sets up in the 3 outsides of inner liner, and extends to end cover 5 departments to both ends, or covers end cover 5. The high-pressure area of the high-pressure hydrogen storage cylinder comprises the interior of the hydrogen storage capillary tube 11, the surface of the tube plate 2 and the inner surface of the end cover 5 at the positions flush with the two ends of the hydrogen storage capillary tube 11, and does not comprise the lining 3 and the 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 compressed hydrogen from the capillary tube bundle 1 is integrated at the air outlet of the second end cap 52. Compared with the conventional container with an opening at one end, the high-pressure hydrogen storage cylinder is simple to operate, avoids frequent opening and closing of ports when a single-port gas cylinder is filled and deflated, and is more convenient to use.
The hydrogen storage capillary tube 11 may be made of any type of high tensile strength glass known in the art, preferably one of magnesium aluminum silicate glass, borosilicate glass, and quartz glass. The cross-sectional shape of the hydrogen storage capillary tube 11 is one of circular, hexagonal, trapezoidal, rectangular, triangular, or elliptical, and the number, end surface shape, and size of the through-holes 23 match with those of the hydrogen storage capillary tube 11. For a given storage pressure, and considering a safety factor, a glass with a higher tensile strength will allow the thickness of the tube sheet 2 to be smaller, while a glass with a lower tensile strength will make the thickness of the tube sheet 2 larger. Typically the outer diameter of the capillary is defined in the range 0.1mm to 8mm and the inner diameter in the range 0.05mm to 7.8 mm. The length of the hydrogen storage capillary tube 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 designed pressure of hydrogen stored in the gas cylinder.
The number of the hydrogen storage capillary tubes 11 may vary from two to several thousand, and the specific number is determined by the size and shape of the gas cylinder and the volume of the gas to be stored in the gas cylinder. The capillaries are arranged parallel to each other. Although the capillary portions outside of the tube sheet 2 are not coated, they are coated with an inner liner 3 of the same material as 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 that of the tube sheet 2, such as polyamide, polyimide, polysulfone, etc. which is chemically compatible with the material of the tube sheet 2. It should be noted that the tube sheet 2 material fills the space between the hydrogen storage capillaries 11 so as to form a gas-tight seal between the hydrogen storage capillaries 11. The tubesheet 2 may be formed from a solid-curable 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 desired shape of the end cap 5. Thus, if the cylinder has a circular cross-sectional shape, or the portion of the end cap 5 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 tube bundle 1 is of a different cross-sectional shape than 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 fit together with a hermetic seal. The thickness of the tube sheet 2 in the axial direction of the hydrogen storage capillary tube 11 may also be varied, 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 capillary tube 11, in combination with the mechanical properties of the material of the tube sheet 2 and the material of the hydrogen storage capillary tube 11, and the size or diameter of the tube sheet 2 and the required 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 bundle 1 is attached to the open end of the end cap 5 to form an air tight 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, the open end of the end cap 5 is adhered to the face 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 surrounding the capillary tube bundle 1 using a sealant such as epoxy. Alternatively, a gas-tight 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 sealing ring 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 plate 2.
The outer shell layer 4 does not constitute a high-pressure environment portion 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 that can withstand high pressure. Typically made of metal, plastic or composite materials. The sheath layer 4 is optionally provided with a pressure relief valve having a set point pressure lower than the design pressure of the gas cylinder, and the enclosed space between the outer surface of the capillary bundle 1 and the inner surface of the sheath layer 4 will never be over-pressurized.
Nothing in this specification is said to apply to the prior art.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.

Claims (13)

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 capillary tubes into a capillary tube bundle; and external compressed hydrogen is connected from one end of the capillary tube bundle, and the hydrogen is stored in each hydrogen storage capillary tube in the capillary tube bundle.
2. The method for storing hydrogen under high pressure as claimed in claim 1, wherein the method for in-situ synthesis of the metal organic framework adsorbent material inside the hydrogen storage capillary is as follows:
s1-1, mixing zinc nitrate Zn (NO)3)2 6H2Dissolving 0 and 4, 4' -benzene-1, 3, 5-triacyl tribenzoic acid in N, N-diethylformamide 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 tiny crystals, and pouring out a 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;
and S1-4, putting the soaked crystal into a vacuum oven, and drying for 6-8 hours at 110-120 ℃ to obtain the metal organic framework adsorbing material distributed in the capillary.
3. The method for high pressure hydrogen storage according to claim 2, wherein the method for in situ synthesis of covalent organic compound adsorbent material inside hydrogen storage capillary is as follows:
s2-1, uniformly mixing the mixed solution of mesitylene and dioxane with tetrakis (4-boraphenyl) methane to form a second solution;
s2-2, enabling the second solution to enter the hydrogen storage capillary tube through vacuumizing, reacting for 80-110 hours at 80-85 ℃ to obtain a 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, thereby obtaining the covalent organic compound adsorbing material distributed in the capillary;
or, the method for in-situ synthesizing the covalent organic compound adsorbing material in the hydrogen storage capillary comprises the following steps:
s3-1, uniformly mixing the mixed solution of mesitylene and dioxane with tetra (4-phenyl borate) silane to form a second solution;
s3-2, enabling the second solution to enter the hydrogen storage capillary tube through vacuum pumping, reacting for 80-110 hours at 80-85 ℃ to obtain a white precipitate II, and pouring out the residual solution;
and S3-3, washing the obtained white precipitate II with anhydrous tetrahydrofuran, and then drying in vacuum at room temperature to remove the solvent, thereby obtaining the covalent organic compound adsorbing material distributed in the capillary.
4. The method for storing hydrogen under high pressure according to claim 3,
zinc nitrate Zn (NO) in the S1-13)2 6H20. The mass/volume ratio of 4, 4' -benzene-1, 3, 5-triacyl tribenzoic acid to N, N-diethylformamide is (17-20 mg) and (3.5-4.5 mg) is 1 mL;
the volume/mass ratio of trimethylbenzene, dioxane and tetra (4-boranophenyl) methane in the S2-1 is 1mL to 1mL (40-60 mg);
the volume/mass ratio of trimethylbenzene, dioxane and tetra (4-phenyl borate) silane in the S3-1 is 3mL to 1mL (50-60 mg).
5. The high-pressure hydrogen storage cylinder is characterized by comprising 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 penetrates through the tube plate (2), two ends of each hydrogen storage capillary (11) are opened, and the end parts of each hydrogen storage capillary (11) are respectively flush with the end surface of the tube plate (2); the two end covers (5) are respectively a first end cover (51) with an air inlet and a second end cover (52) with an air outlet, the open end of the first end cover (51) is connected with the end face of the tube plate (2) at one end of the capillary tube bundle (1) in a sealing mode, the open end of the second end cover (52) is connected with the end face of the tube plate (2) at the other end of the capillary tube bundle (1) in a sealing mode, and the two ends of the hydrogen storage capillary tube (11) are respectively communicated with the first end cover (51) and the second end cover (52).
6. The high-pressure hydrogen storage cylinder according to claim 5, characterized in that the tube plate (2) is provided with a plurality of through holes (23) vertically penetrating through the tube plate (2), and each hydrogen storage capillary (11) in the capillary tube bundle (1) correspondingly penetrates through each through hole (23).
7. The high-pressure hydrogen storage cylinder according to claim 5, characterized in that 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 cap (51), the lower end face of the second tube plate (22) corresponds to the second end cap (52), and each hydrogen storage capillary (11) of the capillary tube bundle (1) passes through the corresponding through hole (23) of the first tube plate (21) and the second tube plate (22), respectively.
8. The high-pressure hydrogen storage cylinder according to claim 5, characterized in that 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), and the outer shell layer (4) is arranged outside the inner liner layer (3) and extends to the end cap (5) from two ends or covers the end cap (5).
9. The high-pressure hydrogen storage cylinder according to claim 5, characterized in that the first adapter (511) for storing externally compressed hydrogen into the capillary tube bundle (1) is integrated at the gas inlet of the first end cap (51), and the 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).
10. The high pressure hydrogen storage cylinder according to claim 5, characterized in that the hydrogen storage capillary tube (11) is one of a magnesium aluminum silicate glass capillary tube, a borosilicate glass capillary tube and a quartz glass capillary tube.
11. The high-pressure hydrogen storage cylinder according to claim 5, characterized in that the cross-sectional shape of the hydrogen storage capillary tube (11) is one of circular, hexagonal, trapezoidal, rectangular, triangular, or elliptical, the diameter or cross-sectional width thereof is 0.1mm to 8mm, and the number, end face shape, and size of the through-holes (23) are matched with the hydrogen storage capillary tube (11); the particle size of the metal organic framework adsorption material or covalent organic compound adsorption material is 1nm-5 mu m.
12. The high pressure hydrogen storage cylinder according to claim 5, 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 have chemical compatibility 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 hydrogen stored in the gas cylinder.
13. The cylinder for storing hydrogen under high pressure according to claim 5, 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 sealingly connected by a complementary thread.
CN202210114509.3A 2022-01-30 2022-01-30 High-pressure hydrogen storage method and gas cylinder Pending CN114427657A (en)

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