CN111609310A - Hydrogen supply device and method for mobile hydrogen filling station - Google Patents
Hydrogen supply device and method for mobile hydrogen filling station Download PDFInfo
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- CN111609310A CN111609310A CN202010625762.6A CN202010625762A CN111609310A CN 111609310 A CN111609310 A CN 111609310A CN 202010625762 A CN202010625762 A CN 202010625762A CN 111609310 A CN111609310 A CN 111609310A
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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
- F17C5/00—Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures
- F17C5/06—Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures for filling with compressed gases
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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
- F17C13/00—Details of vessels or of the filling or discharging of vessels
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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
- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/01—Pure fluids
- F17C2221/012—Hydrogen
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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
- 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
- F17C2223/035—High pressure (>10 bar)
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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
- F17C2227/00—Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
- F17C2227/03—Heat exchange with the fluid
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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
- F17C2227/00—Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
- F17C2227/04—Methods for emptying or filling
- F17C2227/046—Methods for emptying or filling by even emptying or filling
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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
- F17C2260/00—Purposes of gas storage and gas handling
- F17C2260/02—Improving properties related to fluid or fluid transfer
- F17C2260/021—Avoiding over pressurising
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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
- F17C2260/00—Purposes of gas storage and gas handling
- F17C2260/04—Reducing risks and environmental impact
- F17C2260/042—Reducing risk of explosion
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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
- F17C2260/00—Purposes of gas storage and gas handling
- F17C2260/04—Reducing risks and environmental impact
- F17C2260/046—Enhancing energy recovery
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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
- F17C2265/00—Effects achieved by gas storage or gas handling
- F17C2265/06—Fluid distribution
- F17C2265/061—Fluid distribution for supply of supplying vehicles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention provides a hydrogen supply device of a mobile hydrogen filling station, which is used for filling hydrogen into a vehicle-mounted hydrogen storage bottle and comprises a hydrogen production system, a solid hydrogen storage system and a heat exchange circulating system; the hydrogen production system is used for producing hydrogen; the hydrogen production system is internally provided with a built-in heat exchange tube for absorbing heat generated by hydrogen production; the solid hydrogen storage system comprises a solid hydrogen storage device A and a solid hydrogen storage device B, and the solid hydrogen storage device A and the solid hydrogen storage device B can provide different filling pressures; the invention also provides a hydrogen supply method, which sequentially comprises the solid hydrogen storage device A, the solid hydrogen storage device B and the hydrogen production system to fill hydrogen into the vehicle-mounted hydrogen storage bottle, so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle is sequentially increased to 10-15MPa, 20-25MPa and 35MPa, and the pressure is stably increased to ensure the safety. In the heat exchange circulating system, the solid-state hydrogen storage device A and the solid-state hydrogen storage device B both utilize the heat emitted by the hydrogen production system in the hydrogen production process, so that resources are fully utilized, the temperature in the inner cavity of the reaction kettle is reduced, and the safety is ensured.
Description
Technical Field
The invention relates to the technical field of hydrogen preparation, in particular to a hydrogen supply device and a hydrogen supply method for a mobile hydrogen station.
Background
The hydrogen adding station is an important hub for connecting upstream hydrogen production and hydrogen transportation and downstream hydrogen for fuel cell automobiles. The networking distribution of the hydrogenation stations is the basic guarantee of large-scale commercialization of the hydrogen fuel cell technology, and the hydrogen transportation is the key for solving the networking reasonable distribution of the hydrogenation stations.
The hydroprocessing stations can be divided into various types according to different classification methods. The device is divided into a fixed hydrogenation station and a mobile hydrogenation station in a construction form. The hydrogen storage state is divided into a liquid hydrogen station and a high-pressure hydrogen station. The device is divided by a filling mode and can be divided into a single-stage filling hydrogen filling station and a multi-stage filling hydrogen filling station. The hydrogen production mode can be divided into a water electrolysis hydrogen production station, a methanol on-site hydrogen production station, a natural gas on-site hydrogen production station, a gasoline on-site hydrogen production station and the like. The hydrogen source is divided into an external hydrogen supply hydrogenation station and an internal hydrogen production hydrogenation station. The hydrogen production in the station comprises hydrogen production by water electrolysis, hydrogen production by natural gas or methanol reforming and the like. In-station hydrogen production can eliminate the high hydrogen transportation cost, but increases the complexity of the hydrogen station system.
The existing hydrogen stations are mainly divided into two types, namely Off-Site hydrogen production (Off-Site) and On-Site hydrogen production (On-Site). The Off-site hydrogen production (Off-site) can meet the hydrogen demand of a large fuel cell vehicle, the hydrogen is guaranteed, the phenomenon of degassing cannot occur, compressed hydrogen of less than 20MPa is conveyed into the station from a production unit by a hydrogen long-tube trailer, and then the compressed hydrogen is pressurized and unloaded to a high-pressure hydrogen storage bottle group in the station by an in-station compressor and is stored at the pressure of not more than 45 MPa. When the vehicle hydrogenates, hydrogen is output from the hydrogen storage cylinder group and is filled into a vehicle-mounted hydrogen storage cylinder of the fuel cell vehicle through a hydrogenation machine. The need for a compressor to pressurize the material involves a significant risk and is costly.
Accordingly, there is a need for improvements in the art.
Disclosure of Invention
The invention aims to provide a high-efficiency hydrogen supply device and method for a mobile hydrogen station.
In order to solve the technical problem, the invention provides a hydrogen supply device of a mobile hydrogen station, which is used for filling hydrogen into a vehicle-mounted hydrogen storage bottle and comprises a hydrogen production system, a solid-state hydrogen storage system and a heat exchange circulating system;
the hydrogen production system is used for producing hydrogen; the hydrogen production system is internally provided with a built-in heat exchange tube for absorbing heat generated by hydrogen production;
the solid hydrogen storage system comprises a solid hydrogen storage device A and a solid hydrogen storage device B, and the solid hydrogen storage device A and the solid hydrogen storage device B can provide different filling pressures;
the hydrogen outlet of the hydrogen production system is connected with a vehicle-mounted hydrogen storage bottle;
the hydrogen discharge outlets of the solid hydrogen storage device A and the solid hydrogen storage device B are connected with a vehicle-mounted hydrogen storage bottle;
a heat exchange circulation channel of the solid hydrogen storage device A for water circulation is arranged in the solid hydrogen storage device A;
a solid hydrogen storage device B heat exchange circulation channel for water circulation is arranged in the solid hydrogen storage device B;
the heat exchange circulating system comprises a built-in heat exchange tube of the hydrogen production system, a water tank, a heat exchange circulating channel of the solid hydrogen storage device A and a heat exchange circulating channel of the solid hydrogen storage device B;
the outlet of the water tank is divided into two paths after passing through the heat exchange tube arranged in the hydrogen production system by a pipeline, and the two paths are respectively communicated with the inlets of the heat exchange circulation channel of the solid hydrogen storage device A and the heat exchange circulation channel of the solid hydrogen storage device B, and the outlets of the heat exchange circulation channel of the solid hydrogen storage device A and the heat exchange circulation channel of the solid hydrogen storage device B are both connected with the inlet of the water tank.
As an improvement of the hydrogen supply device of the mobile hydrogen station of the invention:
hydrogen generated by the solid hydrogen storage device A is conveyed to the vehicle-mounted hydrogen storage bottle, so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle can reach 10-15 MPa;
hydrogen generated by the solid hydrogen storage device A is conveyed to the vehicle-mounted hydrogen storage bottle, so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle can reach 20-25 MPa;
hydrogen generated by the hydrogen production system is firstly conveyed to the high-pressure hydrogen storage bottle, and the high-pressure hydrogen storage bottle is conveyed to the vehicle-mounted hydrogen storage bottle, so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle can reach 35 MPa.
As a further improvement of the hydrogen supply device of the mobile hydrogen station of the invention:
the hydrogen production system comprises a waste liquid tank, a reaction kettle, a cooling water tank, a dryer and a high-pressure hydrogen storage tank;
the heat exchange tube arranged in the hydrogen production system is arranged in the inner cavity of the reaction kettle;
a solution outlet of the waste liquid tank is connected with an inlet at the upper part of the reaction kettle through a metering pump;
the gas outlet of the reaction kettle is connected with the gas inlet of the high-pressure hydrogen storage tank after sequentially passing through the cooling water tank and the dryer, and the gas outlet of the high-pressure hydrogen storage tank is connected with the vehicle-mounted hydrogen storage bottle;
the bottom of the reaction kettle is communicated with the top of the waste liquid tank through a pipeline.
As a further improvement of the hydrogen supply device of the mobile hydrogen station of the invention:
an overflow valve is arranged between the reaction kettle and the cooling water tank.
The invention also provides a hydrogen supply method, which comprises the following steps:
1) the hydrogen production system is used for producing hydrogen, the normal temperature solution in the heat exchange tube arranged in the hydrogen production system absorbs the heat emitted in the process of producing hydrogen, and the normal temperature solution is changed into a high temperature solution;
2) the high-temperature solution flows out of the heat exchange tube arranged in the hydrogen production system, is divided into two paths and respectively enters the heat exchange circulating channel of the solid hydrogen storage device A and the heat exchange circulating channel of the solid hydrogen storage device B;
the solid hydrogen storage device A and the solid hydrogen storage device B absorb the heat of the high-temperature solution to release hydrogen, and the high-temperature solution is changed into a normal-temperature solution;
3) the normal temperature solution flows out from outlets in a heat exchange circulation channel of the solid hydrogen storage device A and a heat exchange circulation channel of the solid hydrogen storage device B and then enters a water tank; the normal temperature solution in the water tank enters a built-in heat exchange tube of the hydrogen production system;
4) and the vehicle-mounted hydrogen storage bottle is sequentially filled with the solid hydrogen storage device A, the solid hydrogen storage device B and hydrogen of the hydrogen production system.
As an improvement of the hydrogen supply method of the present invention:
step 4 comprises the following steps:
4.1) filling hydrogen generated by the solid hydrogen storage device A into a vehicle-mounted hydrogen storage bottle to ensure that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle reaches 10-15 MPa;
4.2) filling hydrogen generated by the solid hydrogen storage device B into the vehicle-mounted hydrogen storage bottle to ensure that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle reaches 20-25 MPa;
4.3) and hydrogen generated by the hydrogen production system is filled into the vehicle-mounted hydrogen storage bottle, so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle reaches 35 MPa.
The hydrogen supply device and the method of the mobile hydrogen station have the technical advantages that:
the hydrogen supply device of the mobile hydrogen station does not need a compressor, and hydrogen is filled into the vehicle-mounted hydrogen storage bottle sequentially through the solid hydrogen storage device A, the solid hydrogen storage device B and the hydrogen production system, so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle is sequentially increased to 10-15MPa, 20-25MPa and 35MPa, and the pressure is stably increased, and the safety is ensured.
In the heat exchange circulating system, the solid hydrogen storage device A and the solid hydrogen storage device B both utilize the heat emitted by the hydrogen production system in the hydrogen production process, so that resources are fully utilized, the temperature in the inner cavity of the reaction kettle is reduced, and the safety is ensured.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic view showing the construction of a hydrogen supplying apparatus of a mobile hydrogen station according to the present invention;
FIG. 2 shows rare earth AB5PCT curve of type alloy at 30 ℃;
FIG. 3 shows a zirconium-based AB2PCT plot of type alloy at 20 ℃.
In the figure: 1. a reaction kettle; 2. an overflow valve; 3. a cooling water tank; 4. a dryer; 5. a high-pressure hydrogen storage tank; 6. a waste liquid tank; 7. a solid hydrogen storage A; 8. a solid hydrogen storage vessel B; 71. a heat exchange circulation channel of the solid hydrogen storage device A; 81. a heat exchange circulation channel of the solid hydrogen storage device B; 9. a water tank; 10. a vehicle-mounted hydrogen storage bottle; 11. heat exchange tubes are arranged in the hydrogen production system.
hydrogen is the hydrogen uptake curve; dehydrogenation is a hydrogen evolution curve; capacity is capacity; the pressure is the pressure.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
the hydrogen production system is used for producing hydrogen; the hydrogen production system is internally provided with a built-in heat exchange tube for absorbing heat generated by hydrogen production;
the solid hydrogen storage system comprises a solid hydrogen storage device A and a solid hydrogen storage device B, and the solid hydrogen storage device A and the solid hydrogen storage device B can provide different filling pressures;
rare earth AB is arranged in the solid hydrogen storage device A5The alloy is provided with a heat exchanger inside, the heat exchange medium is water, the pressure of a hydrogen platform of the alloy is 12.6MPa at 60 ℃, and the pressure of the hydrogen platform of the alloy is 15.8MPa at 80 ℃. Rare earth AB5The PCT curve of the type alloy at 30 ℃ is shown in figure 2, and the hydrogen discharging platform pressure of the alloy is 3.57 MPa.
The solid hydrogen storage device B is internally provided with a zirconium-based AB2The alloy is provided with a heat exchanger inside, the heat exchange medium is water, the pressure of a hydrogen platform of the alloy is 20.5MPa at 60 ℃, and the pressure of the hydrogen platform of the alloy is 26.6MPa at 80 ℃. Zirconium based AB2The PCT curve of the type alloy at 20 ℃ is shown in figure 3, and the hydrogen discharging platform pressure of the alloy is 8.95 MPa.
The hydrogen outlet of the hydrogen production system is connected with a vehicle-mounted hydrogen storage bottle;
the hydrogen discharge outlets of the solid hydrogen storage device A and the solid hydrogen storage device B are connected with a vehicle-mounted hydrogen storage bottle;
a heat exchange circulation channel of the solid hydrogen storage device A for water circulation is arranged in the solid hydrogen storage device A;
a solid hydrogen storage device B heat exchange circulation channel for water circulation is arranged in the solid hydrogen storage device B;
the heat exchange circulating system comprises a built-in heat exchange tube of the hydrogen production system, a water tank, a heat exchange circulating channel of the solid hydrogen storage device A and a heat exchange circulating channel of the solid hydrogen storage device B;
the outlet of the water tank is divided into two paths after passing through the heat exchange tube arranged in the hydrogen production system by a pipeline, and the two paths are respectively communicated with the inlets of the heat exchange circulation channel of the solid hydrogen storage device A and the heat exchange circulation channel of the solid hydrogen storage device B, and the outlets of the heat exchange circulation channel of the solid hydrogen storage device A and the heat exchange circulation channel of the solid hydrogen storage device B are both connected with the inlet of the water tank.
Hydrogen generated by the solid hydrogen storage device A is conveyed to the vehicle-mounted hydrogen storage bottle, so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle can reach 10-15 MPa;
hydrogen generated by the solid hydrogen storage device A is conveyed to the vehicle-mounted hydrogen storage bottle, so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle can reach 20-25 MPa;
hydrogen generated by the hydrogen production system is firstly conveyed to the high-pressure hydrogen storage bottle, and the high-pressure hydrogen storage bottle is conveyed to the vehicle-mounted hydrogen storage bottle, so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle can reach 35 MPa.
As a further improvement of the hydrogen supply device of the mobile hydrogen station of the invention:
the hydrogen production system comprises a waste liquid tank, a reaction kettle, a cooling water tank, a dryer and a high-pressure hydrogen storage tank;
liquid materials are stored in the waste liquid tank, and solid materials are stored in the reaction kettle;
taking the aluminum-base hydrolysis hydrogen production reaction as an example, the reaction process releases heat:
2Al+2NaOH+6H2O＝2NaAl(OH)4+3H2(1)
the solid material is metal aluminum wire, aluminum powder, aluminum sheet or aluminum scrap, and is processed into a transportable form. The liquid material is NaOH solution with the concentration of 5-20 wt% and is stored in a waste liquid tank.
The heat exchange tube arranged in the hydrogen production system is arranged in the inner cavity of the reaction kettle;
a solution outlet of the waste liquid tank is connected with an inlet at the upper part of the reaction kettle through a metering pump;
the gas outlet of the reaction kettle is connected with the gas inlet of the high-pressure hydrogen storage tank after sequentially passing through the cooling water tank and the dryer, and the gas outlet of the high-pressure hydrogen storage tank is connected with the vehicle-mounted hydrogen storage bottle;
the bottom of the reaction kettle is communicated with the top of the waste liquid tank through a pipeline.
NaAl (OH) obtained by reaction in a reaction kettle4Discharging the solution into a waste liquor tank again, and cooling to perform crystallization reaction (2) to obtain Al (OH)3Precipitate and NaOH solution, and the NaOH solution can be recycled.
NaAl(OH)4＝Al(OH)3+NaOH (2)
An overflow valve 2 is arranged between the reaction kettle and the cooling water tank.
The hydrogen supply method of the hydrogen supply device utilizing the mobile hydrogen station comprises the following steps:
1) the hydrogen production system is used for producing hydrogen, the normal temperature solution in the heat exchange tube arranged in the hydrogen production system absorbs the heat emitted in the process of producing hydrogen, and the normal temperature solution is changed into a high temperature solution;
2) the high-temperature solution flows out of the heat exchange tube arranged in the hydrogen production system, is divided into two paths and respectively enters the heat exchange circulating channel of the solid hydrogen storage device A and the heat exchange circulating channel of the solid hydrogen storage device B;
the solid hydrogen storage device A and the solid hydrogen storage device B absorb the heat of the high-temperature solution to release hydrogen, and the high-temperature solution is changed into a normal-temperature solution;
3) the normal temperature solution flows out from outlets in a heat exchange circulation channel of the solid hydrogen storage device A and a heat exchange circulation channel of the solid hydrogen storage device B and then enters a water tank; the normal temperature solution in the water tank enters a built-in heat exchange tube of the hydrogen production system;
4) and the vehicle-mounted hydrogen storage bottle is sequentially filled with the solid hydrogen storage device A, the solid hydrogen storage device B and hydrogen of the hydrogen production system. The method specifically comprises the following steps:
4.1) filling hydrogen generated by the solid hydrogen storage device A into a vehicle-mounted hydrogen storage bottle to ensure that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle reaches 10-15 MPa;
4.2) filling hydrogen generated by the solid hydrogen storage device B into the vehicle-mounted hydrogen storage bottle to ensure that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle reaches 20-25 MPa;
4.3) and hydrogen generated by the hydrogen production system is filled into the vehicle-mounted hydrogen storage bottle, so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle reaches 35 MPa.
Example 1 experiment 1 using the hydrogen supply apparatus and method of the mobile hydrogen station of the present invention:
the heat generated by the aluminum-base hydrolysis hydrogen production reaction in the hydrogen production system is 277kJ/mol per mol of hydrogen, and the heat required by the solid hydrogen storage device is as follows: 25-30kJ/mol are required for releasing each mol of hydrogen. The heat required for solid-state hydrogen storage device a and solid-state hydrogen storage device B is the heat generated by the hydrogen production reaction (70-80%) taking into account the losses during the heat exchange (70-80% as calculated).
The hydrogen production system starts to produce hydrogen, the generated heat is provided for the solid-state hydrogen storage device A and the solid-state hydrogen storage device B, when the temperature of the solid-state hydrogen storage device A reaches 80 ℃, the pressure of a hydrogen discharging platform of the solid-state hydrogen storage device A is 15.8MPa, the solid-state hydrogen storage device A starts to supply hydrogen to the vehicle-mounted hydrogen storage bottle, and the hydrogen production system continuously supplies heat to the solid-state hydrogen storage device A until the pressure of the vehicle-mounted hydrogen storage bottle reaches 15.8 MPa. When the temperature of the solid-state hydrogen storage device B reaches 80 ℃, the pressure of a hydrogen discharging platform of the solid-state hydrogen storage device B is 25.5MPa, the solid-state hydrogen storage device B starts to supply hydrogen to the vehicle-mounted hydrogen storage bottle, and the hydrogen production system continuously supplies heat to the solid-state hydrogen storage device B until the pressure of the vehicle-mounted hydrogen storage bottle reaches 23.5 MPa. The pressure of a storage tank of the hydrogen production system reaches 40MPa, and the hydrogen production system supplies hydrogen to the vehicle-mounted hydrogen storage bottle until the pressure of the vehicle-mounted hydrogen storage bottle reaches 35 MPa.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (6)
1. The hydrogen supply device of the mobile hydrogen filling station is used for filling hydrogen into a vehicle-mounted hydrogen storage bottle (10), and is characterized in that: comprises a hydrogen production system, a solid-state hydrogen storage system and a heat exchange circulating system;
the hydrogen production system is used for producing hydrogen; a built-in heat exchange tube (11) of the hydrogen production system for absorbing heat generated by hydrogen production is arranged in the hydrogen production system;
the solid-state hydrogen storage system comprises a solid-state hydrogen storage device A (7) and a solid-state hydrogen storage device B (8), and the solid-state hydrogen storage device A (7) and the solid-state hydrogen storage device B (8) can provide different filling pressures;
the hydrogen outlet of the hydrogen production system is connected with a vehicle-mounted hydrogen storage bottle (10);
the hydrogen discharge outlets of the solid hydrogen storage device A (7) and the solid hydrogen storage device B (8) are connected with a vehicle-mounted hydrogen storage bottle (10);
a heat exchange circulating channel (71) of the solid hydrogen storage device A for water circulation is arranged in the solid hydrogen storage device A (7);
a solid hydrogen storage device B heat exchange circulating channel (81) for water circulation is arranged in the solid hydrogen storage device B (8);
the heat exchange circulating system comprises a built-in heat exchange tube (11) of the hydrogen production system, a water tank (9), a heat exchange circulating channel (71) of the solid-state hydrogen storage device A and a heat exchange circulating channel (81) of the solid-state hydrogen storage device B;
the outlet of the water tank (9) is divided into two paths after passing through a built-in heat exchange tube (11) of the hydrogen production system through a pipeline, and the two paths are respectively communicated with the inlets of a heat exchange circulating channel (71) of the solid hydrogen storage device A and a heat exchange circulating channel (81) of the solid hydrogen storage device B, and the outlets of the heat exchange circulating channel (71) of the solid hydrogen storage device A and the heat exchange circulating channel (81) of the solid hydrogen storage device B are both connected with the inlet of the water tank (9).
2. A hydrogen supplying apparatus of a mobile hydrogen station according to claim 1, characterized in that:
hydrogen generated by the solid hydrogen storage device A (7) is transmitted to the vehicle-mounted hydrogen storage bottle (10), so that the hydrogen in the vehicle-mounted hydrogen storage bottle (10) can reach the pressure of 10-15 MPa;
hydrogen generated by the solid hydrogen storage device A (7) is transmitted to the vehicle-mounted hydrogen storage bottle (10), so that the hydrogen in the vehicle-mounted hydrogen storage bottle (10) can reach the pressure of 20-25 MPa;
the hydrogen produced by the hydrogen production system is firstly delivered to the high-pressure hydrogen storage bottle (5), and the high-pressure hydrogen storage bottle (5) is delivered to the vehicle-mounted hydrogen storage bottle (10), so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle (10) can reach 35 MPa.
3. A hydrogen supplying apparatus of a mobile hydrogen station according to claim 2, characterized in that:
the hydrogen production system comprises a waste liquid tank (6), a reaction kettle (1), a cooling water tank (3), a dryer (4) and a high-pressure hydrogen storage tank (5);
the built-in heat exchange tube (11) of the hydrogen production system is arranged in the inner cavity of the reaction kettle (1);
a solution outlet of the waste liquid tank (6) is connected with an inlet at the upper part of the reaction kettle (1) through a metering pump;
the gas outlet of the reaction kettle (1) is connected with the gas inlet of a high-pressure hydrogen storage tank (5) after sequentially passing through a cooling water tank (3) and a dryer (4), and the gas outlet of the high-pressure hydrogen storage tank (5) is connected with a vehicle-mounted hydrogen storage bottle (10);
the bottom of the reaction kettle (1) is communicated with the top of the waste liquid tank (6) through a pipeline.
4. A hydrogen supply device of a mobile hydrogen station according to claim 3, characterized in that:
an overflow valve (2) is arranged between the reaction kettle (1) and the cooling water tank (3).
5. A hydrogen supply method using a hydrogen supply apparatus of a mobile hydrogen station according to any one of claims 1 to 4, characterized in that: the method comprises the following steps:
1) the hydrogen production system is used for producing hydrogen, the normal temperature solution in the built-in heat exchange tube (11) of the hydrogen production system absorbs the heat emitted in the process of producing hydrogen, and the normal temperature solution is changed into a high temperature solution;
2) the high-temperature solution flows out of a heat exchange tube (11) arranged in the hydrogen production system and is divided into two paths which respectively enter a heat exchange circulating channel (71) of a solid hydrogen storage device A and a heat exchange circulating channel (81) of a solid hydrogen storage device B;
the solid hydrogen storage device A (7) and the solid hydrogen storage device B (8) absorb the heat of the high-temperature solution to release hydrogen, and the high-temperature solution becomes a normal-temperature solution;
3) the normal temperature solution flows out from outlets in a heat exchange circulation channel (71) of the solid hydrogen storage device A and a heat exchange circulation channel (81) of the solid hydrogen storage device B and then enters a water tank (9); the normal temperature solution in the water tank (9) enters a built-in heat exchange tube (11) of the hydrogen production system;
4) and the vehicle-mounted hydrogen storage bottle (10) is sequentially filled with the solid hydrogen storage device A (7), the solid hydrogen storage device B (8) and hydrogen of the hydrogen production system.
6. The hydrogen hydrogenation supply method according to claim 5, characterized in that:
the step (4) comprises the following steps:
4.1) filling hydrogen generated by the solid hydrogen storage device A (7) into the vehicle-mounted hydrogen storage bottle (10) so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle (10) reaches 10-15 MPa;
4.2) filling hydrogen generated by the solid hydrogen storage device B (8) into the vehicle-mounted hydrogen storage bottle (10) so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle (10) reaches 20-25 MPa;
4.3) and hydrogen generated by the hydrogen production system is filled into the vehicle-mounted hydrogen storage bottle (10), so that the pressure of the hydrogen in the vehicle-mounted hydrogen storage bottle (10) reaches 35 MPa.
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