CN117346060A - Solid hydrogen energy storage device - Google Patents

Solid hydrogen energy storage device Download PDF

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Publication number
CN117346060A
CN117346060A CN202311185294.5A CN202311185294A CN117346060A CN 117346060 A CN117346060 A CN 117346060A CN 202311185294 A CN202311185294 A CN 202311185294A CN 117346060 A CN117346060 A CN 117346060A
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Prior art keywords
hydrogen
hydrogen storage
solid
valve
tube
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CN202311185294.5A
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Inventor
费万成
唐镜舜
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Shenzhen Shentong Shihua Engineering Equipment Co ltd
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Shenzhen Shentong Shihua Engineering Equipment Co ltd
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Priority to CN202311185294.5A priority Critical patent/CN117346060A/en
Publication of CN117346060A publication Critical patent/CN117346060A/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
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/083—Separating products
    • 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
    • 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
    • F17C13/02—Special adaptations of indicating, measuring, or monitoring equipment
    • 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
    • F17C13/02—Special adaptations of indicating, measuring, or monitoring equipment
    • F17C13/025—Special adaptations of indicating, measuring, or monitoring equipment having the pressure as the parameter
    • 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
    • F17C13/02—Special adaptations of indicating, measuring, or monitoring equipment
    • F17C13/026—Special adaptations of indicating, measuring, or monitoring equipment having the temperature as the parameter
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/04—Hydrogen absorbing
    • 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
    • F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
    • F17C2250/04—Indicating or measuring of parameters as input values
    • F17C2250/0404—Parameters indicated or measured
    • 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
    • F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
    • F17C2250/04—Indicating or measuring of parameters as input values
    • F17C2250/0404—Parameters indicated or measured
    • F17C2250/043—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
    • F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
    • F17C2250/04—Indicating or measuring of parameters as input values
    • F17C2250/0404—Parameters indicated or measured
    • F17C2250/0439—Temperature

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Fuel Cell (AREA)

Abstract

The invention discloses a solid hydrogen energy storage device, which comprises a tank body, a hydrogen storage unit and a control system, wherein the hydrogen storage unit comprises a plurality of hydrogen storage pipes and a hydrogen pipeline, the hydrogen storage pipes are inserted into the tank body, and the tank body is filled with cooling water; the hydrogen storage tube comprises an outer tube and an inner tube, and the outer tube is an slender tube; the inner pipe is inserted into the outer pipe, a powdery solid hydrogen storage material is filled between the outer pipe and the inner pipe, the side wall of the inner pipe comprises a plurality of vent holes, and the outer wall of the inner pipe in the outer pipe is covered by a filter screen; the outer ends of the hydrogen storage pipes are exposed outside the tank body, the openings of the outer ends of the inner pipes of all the hydrogen storage pipes are connected in parallel through hydrogen pipelines, the air inlets of the hydrogen pipelines are connected with air inlet valves, and the air outlets of the hydrogen pipelines are connected with air release valves. The hydrogen storage tube of the solid hydrogen energy storage device adopts the outer tube filled with the powdery solid hydrogen storage material, the outer tube is an elongated tube, the specific area of the solid hydrogen storage material for absorbing hydrogen and exchanging heat is large, the hydrogen storage tube is immersed in cooling water, the heat dissipation is good, the hydrogen absorption efficiency of the hydrogen storage unit is good, and the hydrogen storage amount is high.

Description

Solid hydrogen energy storage device
Technical Field
The invention relates to renewable energy sources, in particular to a solid hydrogen energy storage device.
Background
In recent years, as greenhouse gas emissions increase, global air temperature continues to warm, and climate problems are increasingly prominent.
Due to the gradual maturity of fuel cell technology and the commercialization popularization of fuel cell automobiles, two-wheelers, forklifts, yachts and the like in recent years, the potential of hydrogen as a power fuel is increasingly valued in various circles, and the hydrogen is expected to occupy 10% of the energy consumption proportion of China in 2050, so that the hydrogen is expected to gradually replace the traditional gasoline and diesel, thoroughly change the power energy of human beings and promote the third energy revolution. At present, hydrogen is mainly produced from natural gas or coal, carbon dioxide is produced in the production process, the hydrogen belongs to 'gray hydrogen', and the currently accepted development direction is to generate 'green hydrogen' by means of solar energy and wind energy, and no carbon dioxide is produced in the production process.
At present, the long-term planning in the development of the hydrogen energy industry is published in 2021-2035, the main production mode of green hydrogen is electrolysis water, energy is provided by electric energy, water molecules are decomposed into hydrogen and oxygen on electrodes, and main production equipment of the electrolysis water is an electrolysis tank. Because of the difficulty in storing a large amount of hydrogen generated by water electrolysis, the solid hydrogen storage materials with titanium alloy and the like as carriers at present are a series of characteristics of high quality, high volume storage density, storage pressure less than 5MPa, high safety, hydrogen absorption and desorption temperature less than 60 ℃, high purity of released hydrogen, suitability for large-scale popularization and application and the like, and are important directions of the development of hydrogen storage and hydrogenation technology. However, in practical application, several key technical problems of hydrogen storage and hydrogenation technologies are still not completely solved, namely, 1, how to increase the hydrogen storage amount of a hydrogen storage unit; 2. the hydrogen storage materials are filled in the hydrogen storage device in a powdery form, so that the heat conduction performance is poor, and the hydrogen absorption and desorption efficiency is affected; 3. the filling pressure of the hydrogenation machine of the conventional hydrogenation station reaches 35MPa, the flow is large, and the national relevant standards of the technical standard of the automobile refueling and air-filling hydrogenation station GB50156-2021 and the like do not allow filling of low-pressure solid hydrogen storage bottles below 5MPa, so that the solid hydrogen storage bottles are difficult to fill, and the product application and industry development of the two-wheeled vehicles, forklift trucks, sightseeing vehicles and the like which adopt the solid hydrogen storage bottles as air sources are severely restricted. 4. Hydrogen belongs to inflammable and explosive products, and how to adopt safety measures to prevent safety accidents in the storage and filling processes is an important research topic for developing hydrogen energy technology.
Disclosure of Invention
The invention aims to solve the technical problem of providing a solid hydrogen energy storage device with good hydrogen absorption efficiency and high hydrogen storage capacity.
In order to solve the technical problems, the invention adopts the technical scheme that the solid-state hydrogen energy storage device comprises a tank body, a hydrogen storage unit and a control system, wherein the control system comprises a controller, an air inlet valve and an air release valve, the solid-state hydrogen energy storage device comprises the tank body and the hydrogen storage unit, the hydrogen storage unit comprises a plurality of hydrogen storage pipes and a hydrogen pipeline connected with the hydrogen storage pipes, and the main body part of the hydrogen storage pipes is inserted into the tank body; the hydrogen storage tube comprises an outer tube and an inner tube, the outer tube is an elongated tube, and two ends of the outer tube are sealed by end plates; the inner pipe passes through an end plate at the outer end of the outer pipe and is inserted into the outer pipe, and cooling water is filled in the tank body; the inner end of the inner tube is closed, a powdery solid hydrogen storage material is filled between the outer tube and the inner tube, the side wall of the inner tube comprises a plurality of vent holes, and the outer wall of the inner tube in the outer tube is covered by a filter screen; the outer ends of the hydrogen storage pipes are exposed outside the tank body, the openings of the outer ends of the inner pipes of all the hydrogen storage pipes are connected in parallel through hydrogen pipelines, the air inlets of the hydrogen pipelines are connected with air inlet valves, and the air outlets of the hydrogen pipelines are connected with air release valves.
In the solid hydrogen energy storage device, the plurality of hydrogen storage tubes of the hydrogen storage unit are arranged in an MxN matrix, N is more than 16, M is more than 16, and the filling volume of the solid hydrogen storage material in the hydrogen storage tubes is 65-75% of the space volume between the outer tube and the inner tube; the inner end of the hydrogen storage tube is supported by a vertical plate in the tank body, and the length-diameter ratio of the outer tube of the hydrogen storage tube is more than 70; the solid hydrogen energy storage device comprises a water cooling system and a water heating system, wherein the water cooling system comprises a water inlet valve and a water outlet valve which are arranged on the tank body; the water heating system comprises an explosion-proof heating rod which is inserted into the cooling water, and the control end of the explosion-proof heating rod is connected with the controller; the air inlet valve and the air outlet valve are electromagnetic valves, and the air outlet of the hydrogen pipeline is connected with the air outlet valve; the control end of the air inlet valve and the control end of the air outlet valve are respectively connected with the controller.
The solid hydrogen energy storage device comprises an explosion-proof heating rod, a controller and a control unit, wherein the explosion-proof heating rod comprises a temperature sensor, and the signal output end of the temperature sensor is connected with the controller; the tank body comprises a manhole, and the explosion-proof heating rod is arranged below the manhole.
The control system comprises a hydrogen alarm, a pressure sensor, a deflation pressure gauge, an air inlet pressure gauge and an emergency pressure relief device, wherein the emergency pressure relief device, the hydrogen alarm and the pressure sensor are respectively arranged on the tank body, and a signal output end of the hydrogen alarm and a signal output end of the pressure sensor are respectively connected with the controller; the air inlet pressure gauge is arranged at the inlet of the air inlet valve, and the air outlet pressure gauge is arranged at the outlet of the air outlet valve; the signal output end of the air inlet pressure gauge and the signal output end of the air outlet pressure gauge are respectively connected with the controller.
The solid hydrogen energy storage device is characterized in that the hydrogen production system is an alkaline electrolyzed water hydrogen production system, the alkaline electrolyzed water hydrogen production system comprises an alkali liquor box, a circulating pump, a filter, an electrolytic tank, an oxygen separator and a hydrogen separator, the inlet of the circulating pump is connected with the alkali liquor box, and the outlet of the circulating pump is connected with the electrolytic tank through the filter; the hydrogen outlet of the electrolytic tank is connected with a hydrogen separator, and the oxygen outlet of the electrolytic tank is connected with an oxygen separator; the hydrogen outlet of the hydrogen separator is connected with a hydrogen pipeline through an air inlet valve.
The solid hydrogen energy storage device comprises a hydrogen fuel cell power generation system and a solid hydrogen storage bottle filling system, and the air release valve comprises a first air release valve and a second air release valve; the hydrogen pipeline is connected with the hydrogen fuel cell power generation system through a first air release valve and is connected with the solid hydrogen storage bottle filling system through a second air release valve.
The solid hydrogen energy storage device comprises a vacuum valve, and a hydrogen pipeline is connected with a vacuum source through the vacuum valve; the hydrogen storage unit stores hydrogen gas and comprises the following steps:
701 Opening a vacuum valve to vacuumize the hydrogen storage unit to a set value;
702 Opening the air inlet valve to input hydrogen into the hydrogen storage unit;
703 Opening the water inlet valve and the water outlet valve, and taking away the heat released by the solid hydrogen storage material by the flow of cooling water in the tank body, so as to accelerate the hydrogen absorption speed of the solid hydrogen storage material.
The solid hydrogen energy storage device comprises a solid hydrogen storage bottle filling system, wherein the solid hydrogen storage bottle filling system comprises an air inflation pipe network, the air inflation pipe network comprises a plurality of quick connectors connected with the solid hydrogen storage bottle, and the air inflation pipe network is connected with a hydrogen pipeline through a second air release valve; when the solid hydrogen storage bottle is inflated, the second air release valve is opened, and meanwhile, the controller is used for starting the anti-explosion heating rod to heat cooling water in the tank body to a set temperature, so that the hydrogen release speed of the solid hydrogen storage material is accelerated, and the filling speed of the solid hydrogen storage bottle is improved.
The solid hydrogen energy storage device comprises the components of 8-10 parts by weight of Ti; 14-16 parts of Zr; 2-4 parts of Ni; 6-8 parts of Mn; v1-3 parts; 3-5 parts of Cr; 7 to 9 parts of Fe and 0.5 to 1.5 parts of Ca.
The preparation method of the solid hydrogen storage material of the solid hydrogen energy storage device comprises the following steps: sequentially adding the components into a smelting furnace according to a proportion, vacuumizing, and filling argon, wherein the pressure reaches 0.4-0.6 bar; heating the smelting furnace to 1950-2050 ℃, preserving heat for 5-15 minutes, and cooling to room temperature within 5-20 minutes; and grinding the alloy to 50-400 meshes by adopting a ball milling process.
The hydrogen storage tube of the solid hydrogen energy storage device adopts the outer tube filled with the powdery solid hydrogen storage material, the outer tube is an elongated tube, the specific area of the solid hydrogen storage material for absorbing hydrogen and exchanging heat is large, the hydrogen storage tube is immersed in cooling water, the heat dissipation is good, the hydrogen absorption efficiency of the hydrogen storage unit is good, and the hydrogen storage amount is high.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a schematic diagram of a skid-mounted hydrogen production, storage and generation apparatus according to an embodiment of the present invention.
FIG. 2 is a top view of a skid-mounted hydrogen production, storage and generation apparatus according to an embodiment of the present invention.
FIG. 3 is a cross-sectional view of a skid-mounted hydrogen production, storage and generation device in accordance with an embodiment of the present invention.
Fig. 4 is a cross-sectional structural view of a hydrogen storage tube according to an embodiment of the present invention.
Fig. 5 is an enlarged view of part of the area i in fig. 4.
Reference numerals illustrate:
a hydrogen storage tube-1; an outer tube-101; inner tube (airway) -102; solid hydrogen storage material-103; small hole-104; a filter screen-105; an intake valve-2; skid-mounted tank body-3; solid hydrogen storage bottle-4; a second purge valve-5; an integrated controller-6; a hydrogen alarm 7; a pressure sensor-8; an explosion-proof heating rod sensor-9; cooling water-10; a deflation manometer-11; an air inlet pressure gauge-12; a tap water inlet valve-13; a tap water drain valve-14; emergency pressure relief device-15; a manhole-16; an alkali liquor tank-18; a circulation pump-19; a filter-20; an electrolytic cell-21; an oxygen separator-22; a hydrogen separator-23; a first purge valve-24; a hydrogen fuel cell power generation system-25; the method comprises the steps of carrying out a first treatment on the surface of the A vacuum valve-27; inflation pipe network-28; a first quick connector-29; a hydrogen pipe-30; a hydrogen gas delivery pipe-31; and a second quick connector-32.
Detailed Description
The skid-mounted hydrogen production, hydrogen storage and hydrogen generation device provided by the embodiment of the invention is shown in fig. 1 to 5, and comprises an alkaline electrolyzed water hydrogen production system, a solid hydrogen energy storage device, a hydrogen fuel cell power generation system 25, a solid hydrogen storage bottle filling system and a control system. Hydrogen generated by the alkaline electrolyzed water hydrogen production system is stored in a solid hydrogen energy storage device, and the solid hydrogen energy storage device can provide hydrogen for a hydrogen fuel cell power generation system 25 to generate power, or can fill hydrogen into the solid hydrogen storage bottle 4 through a filling system.
The control system comprises an integrated controller 6, an air inlet valve 2, an air release valve, a hydrogen alarm 7, a pressure sensor 8, an air release pressure gauge 11, an air inlet pressure gauge 12 and an emergency pressure relief device 15.
The solid hydrogen energy storage device comprises a skid-mounted tank body 3, a hydrogen storage unit, a water cooling system and a water heating system. The hydrogen storage unit includes 400 hydrogen storage tubes 1 and a hydrogen pipe 30 connecting all the hydrogen storage tubes 1, and a main body portion of the hydrogen storage tube 1 is inserted into the tank 3. The 400 hydrogen storage tubes 1 of the hydrogen storage unit are arranged in a matrix of m×n, where m=n=20. The inner end of the hydrogen storage tube 1 is supported by a riser 301 in the tank 3.
As shown in fig. 4 and 5, the hydrogen storage tube 1 includes an outer tube 101 and an inner tube (gas guide tube) 102, both ends of the outer tube 101 being closed with end plates. The inner tube 102 is inserted into the outer tube 101 through an end plate at the outer end of the outer tube 101. The inner end of the inner tube 102 is closed, a powdery solid hydrogen storage material 103 is filled between the outer tube 101 and the inner tube 102, a plurality of ventilation small holes 104 are formed in the side wall of the inner tube 102, the outer wall of the inner tube 102 in the outer tube 101 is wrapped by a 400-mesh filter screen 105, and the filter screen 105 can prevent powder of the solid hydrogen storage material 103 from blocking the small holes 104 on the side wall of the inner tube 102 or entering the small holes 104 in the hydrogen discharging process. The outer ends of the hydrogen storage tubes 1 are exposed outside the tank body 3, the openings of the outer ends of the inner tubes 102 of all the hydrogen storage tubes 1 are connected in parallel through the hydrogen pipelines 30, the air inlets of the hydrogen pipelines 30 are connected with the hydrogen outlet of the alkaline electrolyzed water hydrogen production system through the air inlet valves 2, and the air outlets of the hydrogen pipelines 30 are connected with the air release valve. When the air inlet valve and the air outlet valve adopt electromagnetic valves, the control end of the air inlet valve 2 and the control end of the air outlet valve are respectively connected with the integrated controller 6.
The solid hydrogen storage material 103 is Ti 0.9 Zr 0.15 Ni 0.3 Mn 0.7 V 0.2 Cr 0.4 Fe 0.8 Ca 0.1 The composite formula technology is adopted, and the content ratio of each metal is Ti: zr: ni: mn: v: cr: fe, ca=9, 15, 3, 7, 2, 4, 8 and 1.
When the solid hydrogen storage material 103 is prepared, 9 parts by weight of Ti are used; zr 15 parts; 3 parts of Ni; mn 7 parts; v2 parts; cr 4 parts; 8 parts of Fe; sequentially adding 1 part of Ca into a smelting furnace, vacuumizing until the pressure is less than-20K Pa, then charging argon gas until the pressure is 0.4-0.6 bar, heating the smelting furnace to 1950-2050 ℃, preserving heat for 5-15 minutes, cooling to room temperature within 5-20 minutes, and grinding the alloy to 50-400 meshes by adopting a ball milling technology. The solid hydrogen storage material prepared by the method has the hydrogen storage density mass ratio reaching 2wt%, the decomposition pressure of hydride generated by the reaction of the solid hydrogen storage material and hydrogen at 20 ℃ is 0.9MPa, and the index is higher than that of similar products by more than 20%.
According to the embodiment of the invention, 400 hydrogen storage tubes 1 filled with solid hydrogen storage materials are adopted, the outer tube 101 of the hydrogen storage tube 1 is an slender tube, the outer tube 101 of the hydrogen storage tube 1 is a tube with the specification DN40, the length L=3 meters, the inner diameter d=40 mm, the length is large, the tube diameter is small, and the specific area of the solid hydrogen storage materials for adsorbing hydrogen and exchanging heat can be increased. The aspect ratio of the outer tube 101 of the hydrogen storage tube 1 is L: d=30: 0.4 =75.
Considering the hydrogen absorption expansion of the solid hydrogen storage material, the solid hydrogen storage material fills 70% of the volume of the space in the volume pipe, the density of the solid hydrogen storage material is 3400Kg/m & mu, the mass hydrogen storage density is 2%, and the total hydrogen storage amount is as follows:
the volume inside each outer tube 101 is 0.2×0.2×3.14159×30=3.8l.
The hydrogen storage amount of each hydrogen storage tube is given by neglecting the volume of the inner tube:
0.0038 m³×70%×3400 Kg/m³×2%=0.18Kg，
the total hydrogen storage amount of 400 hydrogen storage tubes of the hydrogen storage unit was 0.18×400=72 Kg.
The water cooling system comprises a water inlet valve 13 and a water outlet valve 14 of tap water arranged on the tank body 3, and the tank body 3 is filled with cooling water 10. The water heating system comprises an explosion-proof heating rod 9, and the tank body 3 is provided with a manhole 16, so that the interior is convenient to clean. The explosion-proof heating rod 9 is arranged below the manhole 16 and is inserted into the cooling water 10, and the control end of the explosion-proof heating rod 9 is connected with the integrated controller 6. The solid hydrogen storage material 103 can release heat in the hydrogen absorption process, and the cooling water 10 flows to take away the heat released by the hydrogen absorption of the solid hydrogen storage material through the water inlet valve 13 and the water outlet valve 14 of the cooling tap water arranged on the tank body 3, so that the hydrogen absorption speed is increased.
Meanwhile, as a great amount of heat is required to be absorbed in the hydrogen releasing process of the solid hydrogen storage material 103, in order to accelerate the hydrogen releasing speed, the tank body 3 is internally provided with the explosion-proof heating rod 9 to heat the cooling water 10, so that the heating function of the water bath is realized. The explosion-proof heating rod 9 is provided with a temperature sensor, and the signal output end of the temperature sensor is connected with the integrated controller 6. Can realize the automatic control function of the heating temperature of 0-80 ℃.
The emergency pressure relief device 15, the hydrogen alarm 7 and the pressure sensor 8 are respectively arranged on the tank body 3, and the signal output end of the hydrogen alarm 7 and the signal output end of the pressure sensor 8 are respectively connected with the integrated controller 6, so that the hydrogen leakage alarm function and the alarm function of exceeding pressure standard in the tank body are realized. An air inlet pressure gauge 12 is arranged at the inlet of the air inlet valve 2, and a signal output end of the air inlet pressure gauge 12 is connected with the integrated controller 6. The air inlet pressure gauge 12 is arranged at the inlet of the air inlet valve 2, and achieves the functions of overpressure alarming and automatically closing the air inlet valve 2. The deflation pressure gauge 11 is arranged at the outlet of the deflation valve, and the signal output end of the deflation pressure gauge 11 is connected with the integrated controller 6, so that the functions of overpressure filling alarm and automatic closing of the deflation valve 5 are realized. If hydrogen leakage occurs, gas is discharged to the atmosphere through the emergency pressure relief device 15, no gas accumulation space exists in the tank body 3, the pressure rise tank body is prevented from being broken, and safe production is ensured.
The alkaline electrolyzed water hydrogen production system comprises an alkali liquor box 18, a circulating pump 19, a filter 20, an electrolytic tank 21, an oxygen separator 22 and a hydrogen separator 23, wherein the inlet of the circulating pump 19 is connected with the alkali liquor box 18, and the outlet of the circulating pump 19 is connected with the electrolytic tank 21 through the filter 20. The hydrogen outlet of the electrolytic tank 21 is connected with a hydrogen separator, and the oxygen outlet of the electrolytic tank 21 is connected with an oxygen separator 22. The hydrogen outlet of the hydrogen separator 23 is connected with a hydrogen pipeline 30 through a hydrogen conveying pipeline 31 and an air inlet valve 2. The alkaline water electrolysis hydrogen production system of the embodiment of the invention utilizes renewable energy sources or alkaline water electrolysis hydrogen production of peak-valley electricity of a user side, an alkaline solution tank is connected with a circulating pump and a filter to convey alkaline solution to an electrolysis tank, and hydrogen is generated after alkaline solution in gas is separated through a hydrogen separator after electrolysis.
The bleed valves include a primary bleed valve 24 and a secondary bleed valve 5. The hydrogen pipeline 30 is connected with the hydrogen fuel cell power generation system 25 through the first air release valve 24 and is connected with the solid hydrogen storage bottle filling system through the second air release valve 5.
The solid hydrogen energy storage device is provided with a vacuum valve 27, and a vacuum input interface of a hydrogen pipeline 30 is externally connected with a vacuum source through the vacuum valve 27 and a quick connector 29.
The hydrogen storage unit of the invention stores hydrogen gas, comprising the following steps:
1) Vacuumizing: the vacuumizing device is connected with the quick connector 29, the valve 27 is opened, and vacuumizing is stopped when the vacuum degree of the hydrogen storage unit reaches-5000 Pa;
2) The hydrogen storage unit is used for air intake: after the pressure of hydrogen generated by alkaline electrolysis water is reduced to 5MPa through a reducing valve, an air inlet valve 2 is opened, the hydrogen enters a hydrogen conveying pipeline 31, and the air inlet valve 2 and the hydrogen pipeline 30 charge the hydrogen into a hydrogen storage pipe 1 filled with solid hydrogen storage materials;
3) Simultaneously, a water inlet valve 13 and a water discharge valve 14 of the cooling tap water are opened, heat released by hydrogen absorption of the solid hydrogen storage material is taken away through the flowing of the cooling tap water in the tank body, and the hydrogen absorption speed of the solid hydrogen storage material is accelerated.
The solid state hydrogen storage bottle filling system of the present invention comprises a gas filling pipe network 28, wherein the gas filling pipe network 28 is provided with 50 quick connectors 32 connected with the solid state hydrogen storage bottles 4, and 50 solid state hydrogen storage bottles 4 can be connected at a time. The aeration pipe network 28 is connected to the hydrogen pipe 30 through the secondary air release valve 5.
When the solid hydrogen storage bottle 4 is inflated, the second air release valve 5 is opened, meanwhile, the explosion-proof heating rod 9 is started through the integrated controller 6 to heat the cooling water 10 in the tank body 3 to the set temperature of 60 ℃, the hydrogen release speed of the solid hydrogen storage material 103 is accelerated, the filling speed of the solid hydrogen storage bottle 4 is improved,
when the hydrogen fuel cell power generation system of the present invention generates power, the purge valve 24 is opened, and the hydrogen stored in the solid hydrogen storage material 103 in the hydrogen storage pipe 1 is supplied to the hydrogen fuel cell power generation system 25 via the hydrogen pipe 30 and the purge valve 24 to generate power.
The skid-mounted hydrogen production, hydrogen storage and hydrogen generation device of the embodiment of the invention relates to alkaline electrolyzed water hydrogen production and hydrogen energy storage based on renewable energy sources or peak-valley electricity of users, and the hydrogen production capacity of the device reaches 300Nm 3 And/h, the mass hydrogen storage density of the solid hydrogen storage material is 2%, and the maximum hydrogen storage amount can be achievedUp to 72Kg, safety, environmental protection, high automation degree, small occupied area and low investment. The skid-mounted hydrogen production, hydrogen storage and hydrogen generation device of the embodiment of the invention can be filled with 50 solid hydrogen storage bottles at a time, and the power of a hydrogen fuel cell reaches 80KW. The embodiment of the invention is based on renewable energy sources to produce green hydrogen, then adopts a solid-state hydrogen storage technology to store energy, adjusts and balances peak-to-valley electricity at the user side through power generation of the hydrogen fuel cell, and solves the technical problem of filling the solid-state hydrogen storage bottle.
The invention can be widely applied to the places such as photovoltaic power generation systems and wind power generation systems, peak-valley electricity energy storage at the user side, distributed energy sources and the like.

Claims (10)

1. The solid hydrogen energy storage device comprises a tank body, a hydrogen storage unit and a control system, wherein the control system comprises a controller, an air inlet valve and an air release valve; the hydrogen storage tube comprises an outer tube and an inner tube, the outer tube is an elongated tube, and two ends of the outer tube are sealed by end plates; the inner pipe passes through an end plate at the outer end of the outer pipe and is inserted into the outer pipe, and cooling water is filled in the tank body; the inner end of the inner tube is closed, a powdery solid hydrogen storage material is filled between the outer tube and the inner tube, the side wall of the inner tube comprises a plurality of vent holes, and the outer wall of the inner tube in the outer tube is covered by a filter screen; the outer ends of the hydrogen storage tubes are exposed outside the tank body, and the openings of the outer ends of the inner tubes of all the hydrogen storage tubes are connected in parallel through hydrogen pipelines, and the air inlets of the hydrogen pipelines are connected with air inlet valves.
2. The solid hydrogen energy storage device according to claim 1, wherein a plurality of hydrogen storage tubes of the hydrogen storage unit are arranged in an M x N matrix, N >16, M >16, and the filling volume of the solid hydrogen storage material in the hydrogen storage tubes is 65% -75% of the space volume between the outer tube and the inner tube; the inner end of the hydrogen storage tube is supported by a vertical plate in the tank body, and the length-diameter ratio of the outer tube of the hydrogen storage tube is more than 70; the solid hydrogen energy storage device comprises a water cooling system and a water heating system, wherein the water cooling system comprises a water inlet valve and a water outlet valve which are arranged on the tank body; the water heating system comprises an explosion-proof heating rod which is inserted into the cooling water, and the control end of the explosion-proof heating rod is connected with the controller; the air inlet valve and the air outlet valve are electromagnetic valves, and the air outlet of the hydrogen pipeline is connected with the air outlet valve; the control end of the air inlet valve and the control end of the air outlet valve are respectively connected with the controller.
3. The solid state hydrogen storage device of claim 2, wherein the explosion-proof heating rod comprises a temperature sensor, and a signal output end of the temperature sensor is connected with the controller; the tank body comprises a manhole, and the explosion-proof heating rod is arranged below the manhole.
4. The solid-state hydrogen energy storage device according to claim 1, wherein the control system comprises a hydrogen alarm, a pressure sensor, a deflation manometer, an air inlet manometer and an emergency pressure relief device, wherein the emergency pressure relief device, the hydrogen alarm and the pressure sensor are respectively arranged on the tank body, and a signal output end of the hydrogen alarm and a signal output end of the pressure sensor are respectively connected with the controller; the air inlet pressure gauge is arranged at the inlet of the air inlet valve, and the air outlet pressure gauge is arranged at the outlet of the air outlet valve; the signal output end of the air inlet pressure gauge and the signal output end of the air outlet pressure gauge are respectively connected with the controller.
5. The solid hydrogen energy storage device according to claim 1, comprising a hydrogen production system, wherein the hydrogen production system is an alkaline electrolyzed water hydrogen production system, the alkaline electrolyzed water hydrogen production system comprises an alkali liquor tank, a circulating pump, a filter, an electrolytic tank, an oxygen separator and a hydrogen separator, the inlet of the circulating pump is connected with the alkali liquor tank, and the outlet of the circulating pump is connected with the electrolytic tank through the filter; the hydrogen outlet of the electrolytic tank is connected with a hydrogen separator, and the oxygen outlet of the electrolytic tank is connected with an oxygen separator; the hydrogen outlet of the hydrogen separator is connected with a hydrogen pipeline through an air inlet valve.
6. The solid state hydrogen storage device of claim 2, comprising a hydrogen fuel cell power generation system and a solid state hydrogen storage bottle fill system, wherein the purge valve comprises a first purge valve and a second purge valve; the hydrogen pipeline is connected with the hydrogen fuel cell power generation system through a first air release valve and is connected with the solid hydrogen storage bottle filling system through a second air release valve.
7. The solid state hydrogen storage device of claim 2, wherein the solid state hydrogen storage device comprises a vacuum valve through which the hydrogen conduit is connected to a vacuum source; the hydrogen storage unit stores hydrogen gas and comprises the following steps:
701 Opening a vacuum valve to vacuumize the hydrogen storage unit to a set value;
702 Opening the air inlet valve to input hydrogen into the hydrogen storage unit;
703 Opening the water inlet valve and the water outlet valve, and taking away the heat released by the solid hydrogen storage material by the flow of cooling water in the tank body, so as to accelerate the hydrogen absorption speed of the solid hydrogen storage material.
8. The solid state hydrogen storage device of claim 6, wherein the solid state hydrogen storage bottle filling system comprises an inflation network comprising a plurality of quick connectors connected to the solid state hydrogen storage bottles, the inflation network being connected to the hydrogen pipeline through a secondary deflation valve; when the solid hydrogen storage bottle is inflated, the second air release valve is opened, and meanwhile, the controller is used for starting the anti-explosion heating rod to heat cooling water in the tank body to a set temperature, so that the hydrogen release speed of the solid hydrogen storage material is accelerated, and the filling speed of the solid hydrogen storage bottle is improved.
9. The solid-state hydrogen storage device of claim 1, wherein the solid-state hydrogen storage material comprises, by weight, 8-10 parts of Ti; 14-16 parts of Zr; 2-4 parts of Ni; 6-8 parts of Mn; v1-3 parts; 3-5 parts of Cr; 7 to 9 parts of Fe and 0.5 to 1.5 parts of Ca.
10. The solid state hydrogen storage device of claim 9, wherein the method of preparing the solid state hydrogen storage material comprises the steps of: sequentially adding the components into a smelting furnace according to a proportion, vacuumizing, and filling argon, wherein the pressure reaches 0.4-0.6 bar; heating the smelting furnace to 1950-2050 ℃, preserving heat for 5-15 minutes, and cooling to room temperature within 5-20 minutes; and grinding the alloy to 50-400 meshes by adopting a ball milling process.
CN202311185294.5A 2023-09-14 2023-09-14 Solid hydrogen energy storage device Pending CN117346060A (en)

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