Hydrogen production, storage and hydrogenation integrated system and method

Abstract

The application discloses a hydrogen production, storage and hydrogenation integrated system and method, which comprises a hydrogen production unit, a hydrogen purification and storage unit and a hydrogen pressurization unit connected in sequence, wherein the hydrogen production unit comprises a skid-mounted natural gas hydrogen production device, a desulfurization device and a CO conversion device connected in sequence; the hydrogen purification and storage unit comprises a heat exchanger, a metal hydride purification device and a first adjustable cold and heat source, the metal hydride purification device is filled with a first solid-state hydrogen storage material and is arranged in the heat exchanger; the first adjustable cold and heat source is connected with the heat exchanger; the hydrogen pressurization unit comprises a second adjustable cold and heat source, a heat exchange device and a metal hydride compressor, the metal hydride compressor is filled with a second solid-state hydrogen storage material, and the second adjustable cold and heat source is connected with the heat exchange device; the hydrogen release plateau pressure of the first solid-state hydrogen storage material is higher than the hydrogen absorption plateau pressure of the second solid-state hydrogen storage material, and the hydrogen release plateau pressure of the second solid-state hydrogen storage material is greater than the hydrogen release plateau pressure of the first solid-state hydrogen storage material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogen production, hydrogen purification, hydrogen storage, hydrogen pressurization and hydrogen production and hydrogenation integrated station, and particularly relates to a hydrogen production, hydrogen storage and hydrogenation integrated system and method. BACKGROUND

[0002] The statements herein merely provide background technology related to the present application, and do not necessarily constitute prior art.

[0003] The development and utilization of hydrogen energy is one of the important ways to ensure national energy security and realize low-carbon transformation. The hydrogen energy industry chain mainly includes hydrogen production, storage, transportation, addition, and use. At present, the typical hydrogenation station in China is mainly an external hydrogen supply hydrogenation station. Hydrogen is transported to the hydrogenation station by a long pipe trailer, pressurized by a hydrogen compressor, and stored in a high-pressure storage tank in the station. Then, the hydrogen is filled into the fuel cell vehicle by a hydrogen filling machine. These hydrogenation stations have problems such as high hydrogen cost, high equipment investment cost and maintenance cost, and high safety risk of high-pressure gaseous hydrogen storage.

[0004] The existing hydrogenation station pressurizes hydrogen by a compressor device. The cost of the compressor device accounts for about 30% of the total investment cost of the hydrogenation station, and the maintenance cost accounts for about 20% of the operation cost of the hydrogenation station. Moreover, hydrogen leakage accidents are related to the compressor. At the same time, the safety risk of high-pressure gaseous hydrogen storage in the station is high. With the continuous development of hydrogenation stations, there is an urgent need for high-safety and low-cost hydrogenation station technology. SUMMARY

[0005] In view of the deficiencies in the prior art, the present application aims to provide a hydrogen production, hydrogen storage and hydrogenation integrated system and method.

[0006] In order to achieve the above-mentioned purpose, the present application is realized by the following technical scheme:

[0007] In a first aspect, the present application provides a hydrogen production, hydrogen storage and hydrogenation integrated system, comprising a hydrogen production unit, a hydrogen purification and storage unit, a hydrogen pressurization unit and a hydrogenation device connected in sequence, wherein,

[0008] The hydrogen production unit comprises a skid-mounted natural gas hydrogen production device, a desulfurization device and a CO shift device connected in sequence;

[0009] The hydrogen purification and storage unit comprises a heat exchanger, a metal hydride purification device and a first adjustable cold heat source. The metal hydride purification device is filled with a first solid hydrogen storage material and is arranged inside the heat exchanger. The first adjustable cold heat source is connected with the heat exchanger;

[0010] The hydrogen pressurizing unit comprises a second adjustable cold heat source, a heat exchange device and a metal hydride compressor, the metal hydride compressor is filled with the second solid-state hydrogen storage material, the second adjustable cold heat source is connected with the heat exchange device, and the hydrogen adding device is connected with the hydrogen pressurizing unit.

[0011] The hydrogen release plateau pressure of the first solid-state hydrogen storage material is higher than the hydrogen absorption plateau pressure of the second solid-state hydrogen storage material, and the hydrogen release plateau pressure of the second solid-state hydrogen storage material is greater than the hydrogen release plateau pressure of the first solid-state hydrogen storage material.

[0012] The present application selects a skid-mounted natural gas reforming hydrogen production process at the hydrogen refueling station to effectively reduce the hydrogen production and transportation cost.

[0013] The existing hydrogen refueling station mainly uses high-pressure hydrogen storage tanks for hydrogen storage, which has small volume hydrogen storage density and great safety hazards, and is prone to leakage and explosion.

[0014] In addition, when hydrogen needs to be released from the solid-state hydrogen storage material, the medium temperature of the first adjustable cold heat source is adjusted, the solid-state hydrogen storage material is heated to a set temperature through the first heat exchanger to release hydrogen, the hydrogen is pressurized, and the release pressure of the hydrogen is adjusted to provide hydrogen with different pressures, which has the advantages of higher safety and lower energy consumption.

[0015] Since the traditional hydrogen pressure increase is generally mechanical pressure increase, the investment cost of the compression equipment is high, and the energy consumption in the hydrogen pressure increase process is high.

[0016] The first solid-state hydrogen storage material can not only play the roles of hydrogen purification and hydrogen storage, but also cooperate with the hydrogen pressurizing unit to realize step-by-step pressurization of hydrogen.

[0017] In some embodiments, the first solid-state hydrogen storage material is La 0.4 Ce 0.4 Ca 0.2 Ni5 alloy, and the second solid-state hydrogen storage material is (Ti 0.97 Zr 0.03 ) 1.1 Cr1.6 Mn 0.4 or ZrFe 1.8 Ni 0.2 alloy.

[0018] The hydrogen purification storage unit is provided with a metal hydride purification device filled with a first solid-state hydrogen storage material La 0.4 Ce 0.4 Ca 0.2 Ni5 alloy, which can selectively adsorb hydrogen and facilitate the discharge of non-hydrogen impurities in the reforming gas, thereby achieving good hydrogen purification effect.

[0019] The solid-state hydrogen storage material used in the application can perform hydrogen absorption reaction at the same temperature and as far as possible ensure that the hydrogen release reaction occurs at the same temperature, so as to achieve the corresponding required plateau pressure, and the heat released by the adjacent metal hydride device can be fully utilized to achieve the purpose of energy saving and consumption reduction.

[0020] The system of the application is used for hydrogenation at a hydrogenation station, and needs to meet 35MPa and 70MPa hydrogen filling. The existing hydrogen storage material is generally only for high-pressure cylinder filling, and can only realize one kind of operating pressure during operation, which is difficult to meet the requirements of the filling station. When the solid-state hydrogen storage material is selected as (Ti 0.97 Zr 0.03 ) 1.1 Cr 1.6 Mn 0.4 or ZrFe 1.8 Ni 0.2 alloy, the hydrogen filling requirements can be more easily met.

[0021] In some embodiments, the number of metal hydride purification devices in the hydrogen purification storage unit is greater than 2, the metal hydride purification devices are arranged in parallel, and an independent heat exchanger is arranged on the outer side of each metal hydride purification device. The number of metal hydride purification devices is greater than 2, which can realize the purification of hydrogen by some purification devices and the pressurized release of hydrogen by some purification devices, so as to ensure the continuous purification, storage and release of hydrogen.

[0022] An independent heat exchanger is arranged on the outer side of each metal hydride purification device, which can independently adjust the temperature of the respective metal hydride purification device to ensure appropriate hydrogen storage and purification temperature and hydrogen release temperature.

[0023] Preferably, the number of metal hydride purification devices is even. In some purifiers, hydrogen absorption reaction occurs, and the remaining purifiers release hydrogen. Then in the next time period, the former releases hydrogen, and the latter absorbs hydrogen, which is repeated to realize continuous purification and purification treatment of the hydrogen containing impurities.

[0024] Preferably, the different metal hydride purifiers are filled with the same hydrogen storage alloy with the same hydrogen absorption and desorption pressure level.

[0025] Preferably, the hydrogen pressurizing unit comprises two-stage pressurizing units connected in series, in the first stage pressurizing unit, the metal hydride compressor is filled with (Ti 0.97 Zr 0.03 ) 1.1 Cr 1.6 Mn 0.4 alloy; in the second stage pressurizing unit, the metal hydride compressor is filled with ZrFe 18 Ni 02 alloy.

[0026] Since the hydrogen filling station needs to realize 35MPa and 70MPa two kinds of pressure hydrogen filling, it is found through experiments that when the metal hydride compressor in the first stage pressurizing unit is filled with (Ti 0.97 Zr 0.03 ) 1.1 Cr 1.6 Mn 0.4 alloy, 35MPa hydrogen can be obtained when the temperature is adjusted to release hydrogen. When 70MPa hydrogen is needed, part of the 35MPa hydrogen can be used for two-stage pressurizing by the second stage pressurizing unit, and when the second stage pressurizing unit is filled with ZrFe 1.8 Ni 0.2 alloy, 70MPa hydrogen can be obtained.

[0027] The three kinds of hydrogen storage alloys used in the application can be connected in series according to reasonable platform pressure, so that the hydrogen absorption platform pressure of the next stage is lower than the hydrogen desorption platform pressure of the previous stage, that is, the multi-stage pressurizing effect can be achieved, so that 35MPa and 70MPa hydrogen filling can be realized.

[0028] Further preferably, the different metal hydride compressors are filled with hydrogen storage alloys with different hydrogen absorption and desorption pressure levels.

[0029] Further preferably, a buffer tank is connected between the first stage pressurizing unit and the second stage pressurizing unit.

[0030] Under the action of the second adjustable cold and heat source, hydrogen absorption reaction occurs in the first stage metal hydride compressor, and the reaction temperature of the first stage metal hydride compressor is set according to the hydrogen filling pressure requirement. Under the action of the second adjustable cold and heat source, hydrogen desorption reaction occurs, realizing hydrogen compression. When 35MPa hydrogen filling is performed, the medium-pressure hydrogen is output to the 35MPa hydrogen filling device for hydrogen filling. When 70MPa hydrogen filling is performed, the medium-pressure hydrogen is output to the buffer tank. When the hydrogen filling station needs to simultaneously perform 35MPa and 70MPa hydrogen filling, the medium-pressure hydrogen can be output to the 35MPa hydrogen filling device, and part of the medium-pressure hydrogen can be output to the buffer tank at the same time.

[0031] The medium-pressure hydrogen gas in the buffer tank is input into the secondary metal hydride compressor, and under the action of the second external adjustable cold heat source, hydrogen absorption reaction occurs in the secondary metal hydride compressor, then, according to the hydrogenation pressure requirement, the reaction temperature of the secondary metal hydride compressor is set, under the action of the second adjustable cold heat source, hydrogen release reaction occurs, and high-pressure hydrogen gas is output to the 70MPa hydrogenation device for hydrogen filling.

[0032] In some embodiments, the heat conduction medium of the first adjustable cold heat source and the second adjustable cold heat source is water or heat conducting oil.

[0033] The system also includes connecting pipelines, valves and equipment control systems between the devices, realizes automatic control and operation monitoring of the hydrogenation process, and ensures the operation safety of the hydrogenation system. Automatic control valves and check valves are arranged on the pipelines connecting the devices, so as to avoid gas backflow.

[0034] In a second aspect, the application provides a hydrogen production, storage and filling integrated method, which comprises the following steps:

[0035] The hydrogen gas produced by the skid-mounted natural gas reforming hydrogen production device after desulfurization and CO shift treatment is input into the metal hydride purifier, hydrogen absorption reaction occurs under the action of the first adjustable cold heat source, metal hydride is generated and stored, and impurity gas is discharged;

[0036] The hydrogen gas stored in the metal hydride purifier releases hydrogen under the heating action of the first adjustable cold heat source, and the generated hydrogen gas is input into the metal hydride compressor;

[0037] Under the action of the second adjustable cold heat source, hydrogen absorption reaction occurs in the metal hydride compressor, according to the hydrogenation pressure requirement, the reaction temperature of the metal hydride compressor is set, hydrogen release reaction occurs, and the pressure of the hydrogen gas is increased.

[0038] In some embodiments, when medium-pressure hydrogen gas filling is performed, the medium-pressure hydrogen gas is output to a medium-pressure hydrogenation device for hydrogen filling;

[0039] Preferably, when high-pressure hydrogen gas filling is performed, the medium-pressure hydrogen gas is output to a buffer tank, the medium-pressure hydrogen gas in the buffer tank is input into the secondary metal hydride compressor to generate hydrogen absorption reaction, then, according to the hydrogenation pressure requirement, the reaction temperature of the secondary metal hydride compressor is set, hydrogen release reaction occurs, and high-pressure hydrogen gas is output.

[0040] Preferably, when simultaneous filling of medium-pressure hydrogen and high-pressure hydrogen is required, the medium-pressure hydrogen is output to a medium-pressure hydrogen filling device for medium-pressure hydrogen filling, and part of the medium-pressure hydrogen is output to a buffer tank, the medium-pressure hydrogen in the buffer tank is introduced into a secondary metal hydride compressor to generate a hydrogen absorption reaction, then, according to the hydrogen filling pressure requirement, the reaction temperature of the secondary metal hydride compressor is adjusted to generate a hydrogen release reaction, and high-pressure hydrogen is output.

[0041] In the hydrogen filling station, the pressure of the medium-pressure hydrogen is generally 35 MPa, and the pressure of the high-pressure hydrogen is generally 70 MPa.

[0042] The beneficial effects achieved by one or more embodiments of the present application are as follows:

[0043] By using the pry-mounted natural gas reforming hydrogen production process to produce hydrogen on site, the cost of hydrogen production and transportation can be reduced, and the metal hydride is used to purify, store and pressurize hydrogen, compared with high-pressure gaseous hydrogen storage and low-temperature liquid hydrogen storage, not only higher-purity hydrogen gas of different pressures can be obtained, but also the safety is higher and the energy consumption is lower.

[0044] The heat management system and the adjustable cold and heat source in the system are used to recycle the heat released during the hydrogen absorption of the solid-state hydrogen storage material, and to reduce the heating energy consumption required during the hydrogen release.

[0045] By using the selective absorption of hydrogen by the solid-state hydrogen storage material, the purification and impurity removal of the hydrogen produced by the hydrogen production unit can be achieved, the metal hydride purification device can continuously release high-purity hydrogen products to meet the use requirements, the use of large-scale purification equipment can be reduced, and the operation is simple, the material cost is low, the equipment and process are relatively simple, the operation is reliable, the occupied area is reduced, and the purity is high.

[0046] The non-mechanical type pressure boosting realized by the heat management system saves the investment cost of the compression equipment and reduces the maintenance and operation cost of the hydrogen filling station, compared with the traditional mechanical hydrogen compressor, the metal hydride compressor has the advantages of safety, environmental protection, no vibration and noise, good sealing, no friction, effective purification of hydrogen, low maintenance cost, etc., and the problems of poor reliability and poor safety of the traditional mechanical pressure boosting method are avoided, and the present application can realize 35 MPa and 70 MPa hydrogen filling simultaneously without mechanical compression.

[0047] In addition, the existing hydrogen filling station mainly uses high-pressure hydrogen storage tanks as the hydrogen storage container in the station, which has small volume hydrogen storage density and has a large safety hazard, is easy to leak and explode. The present application uses solid-state metal hydrogen storage to store the produced hydrogen, which not only improves the volume hydrogen storage density, but also improves the safety and operability of the equipment. BRIEF DESCRIPTION OF DRAWINGS

[0048] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0049] Figure 1 This is a schematic diagram of the three-stage metal hydride compression process in an embodiment of the present invention;

[0050] In the diagram, P L For low temperature T L The hydrogen absorption plateau pressure below; P H For high temperature T H The hydrogen desorption plateau pressure below;

[0051] Figure 2 This is a schematic diagram of an integrated hydrogen production, storage, and refueling system in an embodiment of the present invention;

[0052] Figure 3 This is a schematic diagram of the integrated hydrogen production, storage and refueling method in an embodiment of the present invention.

[0053] In the diagram, 1-hydrogen production unit, 2-first heat exchanger, 3-first metal hydride purifier, 4-second heat exchanger, 5-second metal hydride purifier, 6-first adjustable heat source, 7-first heat exchange device, 8-first-stage metal hydride compressor, 9-buffer tank, 10-second heat exchange device, 11-second-stage metal hydride compressor, 12-second adjustable heat source, 13-35MPa hydrogen refueling device, 14-70MPa hydrogen refueling device. Detailed Implementation

[0054] It should be noted that the following detailed description is illustrative and intended to provide further explanation of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0055] The present invention will be further described below with reference to the embodiments.

[0056] like Figure 1 As shown, the principle of the three-stage metal hydride compression process is as follows: at a temperature of T... L At this point, the hydrogen storage alloy has a relatively low hydrogen absorption plateau pressure. When the input hydrogen pressure exceeds this plateau pressure, the alloy begins to absorb hydrogen. Then, the temperature of the hydrogen storage alloy is raised to T by heating the medium. HAt this time, the alloy has a high hydrogen release plateau pressure, and the cavity hydrogen pressure is much lower than the hydrogen release plateau pressure, so the alloy releases hydrogen until the output hydrogen pressure reaches the hydrogen release plateau pressure. By matching the plateau pressures of several hydrogen storage alloys and connecting them in series, the hydrogen absorption plateau pressure of the next stage is lower than the hydrogen release plateau pressure of the previous stage, thereby achieving a multi-stage pressurization effect. In the present application, three kinds of hydrogen storage alloys can be connected in series according to reasonable plateau pressures, so that the hydrogen absorption plateau pressure of the next stage is lower than the hydrogen release plateau pressure of the previous stage, thereby achieving a multi-stage pressurization effect, and 35MPa and 70MPa hydrogen filling can be realized.

[0057] As shown in Figure 2 According to one aspect of the present application, a hydrogen production, storage and hydrogen filling integrated system is provided, which comprises a hydrogen production unit 1, a metal hydride purification device, a metal hydride compression device and a 35MPa hydrogen filling device 13 and a 70MPa hydrogen filling device 14.

[0058] The metal hydride purification device comprises a first heat exchanger 2, a first metal hydride purifier 3, a second heat exchanger 4, a second metal hydride purifier 5 and a first adjustable cold heat source 6.

[0059] The metal hydride compression device comprises a third heat exchanger 7, a first-stage metal hydride compressor 8, a buffer tank 9, a fourth heat exchanger 10, a second-stage metal hydride compressor 11 and a second adjustable cold heat source 12.

[0060] The outlet of the hydrogen production unit 1 is connected to the inlets of the first metal hydride purifier 3 and the second metal hydride purifier 5; the outlets of the first metal hydride purifier 3 and the second metal hydride purifier 5 are connected to the inlet of the first-stage metal hydride compressor 8; the outlet of the first-stage metal hydride compressor 8 is connected to the inlet of the buffer tank 9 and the inlet of the 35MPa hydrogen filling device 13, respectively; the outlet of the buffer tank 9 is connected to the inlet of the second-stage metal hydride compressor 11; and the outlet of the second-stage metal hydride compressor 11 is connected to the inlet of the 70MPa hydrogen filling device 14.

[0061] A heat management system is provided between adjacent two metal hydride devices, which comprises a heat exchanger, an adjustable cold heat source and a temperature control system. The heat management system is used to store the heat released when the metal hydride device releases hydrogen, and to provide heat when the adjacent metal hydride device stores hydrogen.

[0062] In an alternative embodiment, the heat transfer medium between the heat management system and each metal hydride device is water or heat conducting oil, but is not limited to these two heat transfer media, as long as the heat management system and the metal solid-state hydrogen storage device can conduct heat.

[0063] The first metal hydride purifier 3 and the second metal hydride purifier 5 are internally provided with the same hydrogen storage alloy of hydrogen absorption and release pressure level, the first-stage metal hydride compressor 8 and the second-stage metal hydride compressor 11 are internally provided with the different hydrogen storage alloy of hydrogen absorption and release pressure level, and the hydrogen storage alloy in the metal hydride purifier is different. By using the different solid-state hydrogen storage alloy, the hydrogen release temperature in the metal hydride device is controlled to be different, and the hydrogen release pressure is also controlled to be different, so as to realize the final hydrogen filling requirements of 35MPa and above 70MPa.

[0064] The solid-state hydrogen storage material in the metal hydride purifier uses La 0.4 Ce 0.4 Ca 0.2 Ni5 alloy, the solid-state hydrogen storage material in the first-stage metal hydride compressor uses (Ti 0.97 Zr 0.03 ) 1.1 Cr 1.6 Mn 0.4 alloy, and the solid-state hydrogen storage material in the second-stage metal hydride compressor uses ZrFe 1.8 Ni 0.2 alloy. The solid-state hydrogen storage material in the application is not limited to the above-mentioned materials, and the solid-state hydrogen storage material can be matched to realize the step-by-step boosting of hydrogen pressure.

[0065] The hydrogen production unit is provided with a hydrogen production unit 1, a first-stage metal hydride purifier 3, a second-stage metal hydride purifier 5, a first-stage metal hydride compressor 8, a second-stage metal hydride compressor 11, a 35MPa hydrogen filling device 13, and a 70MPa hydrogen filling device 14.

[0066] The hydrogen production unit 1 adopts a skid-mounted natural gas reforming hydrogen production device to produce hydrogen in the hydrogen filling station. The hydrogen production in the hydrogen filling station not only saves the cost of the expensive hydrogen transportation link, but also greatly reduces the cost of hydrogen. The hydrogen production process in the hydrogen production unit 1 includes a pre-desulfurization process and a post-CO conversion process, which can ensure the service life and performance of the subsequent metal hydride device.

[0067] In an alternative embodiment, the 35MPa hydrogen filling device 13 includes at least one hydrogen filling machine, the 70MPa hydrogen filling device 14 includes at least one hydrogen filling machine, and the hydrogen filling machine is provided with a hydrogen filling gun to realize hydrogen filling.

[0068] In addition to the above main equipment, the system further comprises connecting pipelines between the equipment, valves and an equipment control system, so as to realize automatic control and operation monitoring of the hydrogenation process and ensure the operation safety of the hydrogenation system.

[0069] The application discloses a hydrogen production, storage and hydrogenation integrated method.

[0070] Hydrogen is produced by a natural gas reforming hydrogen production device of the hydrogen production unit 1, and the gas needs to be subjected to desulfurization treatment before reaction.

[0071] The produced hydrogen is introduced into the metal hydride purifier, under the action of the first adjustable cold heat source 6, the first metal hydride purifier 3 (or the second metal hydride purifier 5) absorbs hydrogen to store hydrogen, and the impurity tail gas after reaction is discharged from the system.

[0072] By arranging a plurality of metal hydride purifiers, the hydrogen absorption and hydrogen release reactions in different metal hydride purifiers are alternately and repeatedly circulated, so that continuous purification and purification treatment of the hydrogen containing impurities are realized.

[0073] The purified high-purity hydrogen is introduced into the first-stage metal hydride compressor 8, under the action of the second adjustable cold heat source 12, absorbs hydrogen to store hydrogen, and according to the hydrogen utilization pressure requirement of the downstream, the reaction temperature of the first-stage metal hydride compressor 8 is set.

[0074] The medium-pressure hydrogen gas is introduced into the second-stage metal hydride compressor 11 through the buffer tank 9, under the action of the second adjustable cold heat source 12, absorbs hydrogen to store hydrogen, and according to the hydrogen utilization pressure requirement of the downstream, the reaction temperature of the second-stage metal hydride compressor 11 is set.

[0075] The high-pressure hydrogen gas is introduced into the 70MPa hydrogenation device 14, and the fuel cell vehicle is filled by the hydrogenation machine.

[0076] In the method, the pipelines between the devices are respectively provided with valves and automatic control systems, so as to realize control and safety guarantee of the system working state.

[0077] According to the method, the metal hydride is used as a medium, the PCT characteristic curve of the hydrogen storage material and the characteristic of being capable of selectively absorbing hydrogen are utilized, high-purity hydrogen is purified from the natural gas reforming gas, the stability is stored in the metal hydride, the hydrogen production and purification device and the subsequent hydrogen storage device are concentrated into one set of device, the land area and the investment cost are saved, meanwhile, the metal hydride has the hydrogen compression function, 35MPa and 70MPa hydrogenation can be simultaneously realized in the same hydrogenation station, and the problems of the hydrogen storage safety, the hydrogen gas pressurization safety, the large land area of the hydrogenation station and the high investment cost are solved.

[0078] The application can be used for the construction of the hydrogenation station, the coupling calculation of the hydrogenation station filling scale, the natural gas reforming hydrogen production and the metal solid-state hydrogen storage and the calculation of cold and heat energy are carried out, each equipment is reasonably configured, the construction investment and the operation cost of the hydrogenation station can be effectively reduced, and the overall safety of the hydrogenation station is improved.

[0079] The above only describes the preferred embodiments of the application and is not used to limit the application, for those skilled in the art, the application can have various changes and variations, any modification, equivalent replacement, improvement and the like within the spirit and principle of the application should be included in the protection scope of the application.

Claims

1. An integrated hydrogen production, storage and addition system, characterized in that: The system comprises sequentially connected hydrogen production unit, hydrogen purification and storage unit, hydrogen pressurization unit and hydrogenation device, wherein, The hydrogen production unit comprises sequentially connected skid-mounted natural gas hydrogen production device, desulfurization device and CO shift device; The hydrogen purification and storage unit comprises heat exchanger, metal hydride purification device and first adjustable cold and heat source, the metal hydride purification device is filled with first solid-state hydrogen storage material and is arranged inside the heat exchanger; the first adjustable cold and heat source is connected with the heat exchanger; The hydrogen pressurization unit comprises second adjustable cold and heat source, heat exchange device and metal hydride compressor, the metal hydride compressor is filled with second solid-state hydrogen storage material, the second adjustable cold and heat source is connected with the heat exchange device, and the hydrogenation device is connected with the hydrogen pressurization unit; The hydrogen release plateau pressure of the first solid-state hydrogen storage material is higher than the hydrogen absorption plateau pressure of the second solid-state hydrogen storage material, and the hydrogen release plateau pressure of the second solid-state hydrogen storage material is greater than the hydrogen release plateau pressure of the first solid-state hydrogen storage material; The first solid-state hydrogen storage material is La 0.4 Ce 0.4 Ca 0.2 Ni5 alloy, and the second solid-state hydrogen storage material is (Ti 0.97 Zr 0.03 ) 1.1 Cr 1.6 Mn 0.4 and ZrFe 1.8 Ni 0.2 alloy; the hydrogen gas pressurizing unit comprises two-stage pressurizing units connected in series, in the first-stage pressurizing unit, the metal hydride compressor is filled with (Ti 0.97 Zr 0.03 ) 1.1 Cr 1.6 Mn 0.4 alloy; in the second-stage pressurizing unit, the metal hydride compressor is filled with ZrFe 1.8 Ni 0.2 alloy; The metal hydride purification device is provided with independent heat exchanger outside.

2. The integrated hydrogen production, storage and addition system of claim 1, wherein: The number of metal hydride purification devices in the hydrogen purification and storage unit is greater than 2, and the metal hydride purification devices are connected in parallel.

3. The integrated hydrogen production, storage and addition system of claim 2, wherein: The number of metal hydride purification devices is even.

4. The integrated hydrogen production, storage and addition system of claim 2, wherein: Different metal hydride purification devices are filled with hydrogen storage alloy with same hydrogen absorption and release pressure grade.

5. The integrated hydrogen production, storage and addition system of claim 1, wherein: The first and second pressurization units are connected with buffer tank.

6. The integrated hydrogen production, storage and addition system of claim 1, wherein: The heat conduction medium of the first and second adjustable cold and heat sources is water or heat conducting oil.

7. An integrated method for hydrogen production, hydrogen storage and hydrogen addition, characterized in that: The system comprises the following steps: Hydrogen produced by skid-mounted natural gas reforming hydrogen production device after desulfurization and CO shift treatment is introduced into the metal hydride purification device, and hydrogen absorption reaction occurs under the action of the first adjustable cold and heat source to generate metal hydride for storage, and impurity gas is discharged; Hydrogen stored in the metal hydride purification device releases hydrogen under the heating action of the first adjustable cold and heat source, and the generated hydrogen is introduced into the metal hydride compressor; Hydrogen absorption reaction occurs in the metal hydride compressor under the action of the second adjustable cold and heat source, the reaction temperature of the metal hydride compressor is set according to the hydrogenation pressure requirement, hydrogen release reaction occurs, and hydrogen is pressurized. 8.The method according to claim 7, wherein: When medium-pressure hydrogen is filled, medium-pressure hydrogen is output to the medium-pressure hydrogenation device for hydrogen filling. 9.The method according to claim 8, wherein: When high-pressure hydrogen is filled, medium-pressure hydrogen is output to the buffer tank, medium-pressure hydrogen in the buffer tank is introduced into the secondary metal hydride compressor to occur hydrogen absorption reaction, then the reaction temperature of the secondary metal hydride compressor is set according to the hydrogenation pressure requirement, hydrogen release reaction occurs, and high-pressure hydrogen is output.

10. The integrated hydrogen production, storage and addition method of claim 9, wherein: When medium-pressure hydrogen and high-pressure hydrogen are filled at the same time, medium-pressure hydrogen is output to the medium-pressure hydrogenation device for medium-pressure hydrogenation, and part of the medium-pressure hydrogen is output to the buffer tank, medium-pressure hydrogen in the buffer tank is introduced into the secondary metal hydride compressor to occur hydrogen absorption reaction, then the reaction temperature of the secondary metal hydride compressor is adjusted according to the hydrogenation pressure requirement, hydrogen release reaction occurs, and high-pressure hydrogen is output.

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