CN117263140A - Hydrogen production, hydrogen storage and hydrogenation integrated system and method - Google Patents
Hydrogen production, hydrogen storage and hydrogenation integrated system and method Download PDFInfo
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- CN117263140A CN117263140A CN202311061308.2A CN202311061308A CN117263140A CN 117263140 A CN117263140 A CN 117263140A CN 202311061308 A CN202311061308 A CN 202311061308A CN 117263140 A CN117263140 A CN 117263140A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 384
- 239000001257 hydrogen Substances 0.000 title claims abstract description 384
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 357
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 76
- 238000003860 storage Methods 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 13
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 120
- 150000004681 metal hydrides Chemical class 0.000 claims abstract description 120
- 239000007787 solid Substances 0.000 claims abstract description 45
- 239000011232 storage material Substances 0.000 claims abstract description 42
- 238000000746 purification Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003345 natural gas Substances 0.000 claims abstract description 11
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 6
- 230000023556 desulfurization Effects 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims description 33
- 229910045601 alloy Inorganic materials 0.000 claims description 29
- 239000000956 alloy Substances 0.000 claims description 29
- 150000002431 hydrogen Chemical class 0.000 claims description 26
- 230000009471 action Effects 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 7
- 238000002407 reforming Methods 0.000 claims description 7
- 238000003795 desorption Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- 230000010354 integration Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 description 8
- 230000006835 compression Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- 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
- C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
- C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
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- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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Abstract
The invention discloses a hydrogen production, hydrogen storage and hydrogenation integrated system and method, comprising a hydrogen production unit, a hydrogen purification storage unit and a hydrogen pressurizing unit which are sequentially connected, wherein the hydrogen production unit comprises a skid-mounted natural gas hydrogen production device, a desulfurization device and a CO conversion device which are sequentially connected; the hydrogen purification storage unit comprises a heat exchanger, a metal hydride purification device and a first adjustable cold and heat source, wherein the metal hydride purification device is filled with a first solid hydrogen storage material which is arranged in the heat exchanger; the first adjustable cold and heat source is connected with the heat exchanger; the hydrogen pressurizing unit comprises a second adjustable cold and heat source, a heat exchange device and a metal hydride compressor, wherein a second solid hydrogen storage material is filled in the metal hydride compressor, and the second adjustable cold and heat source is connected with the heat exchange device; the hydrogen releasing platform pressure of the first solid hydrogen storage material is higher than the hydrogen absorbing platform pressure of the second solid hydrogen storage material, and the hydrogen releasing platform pressure of the second solid hydrogen storage material is higher than the hydrogen releasing platform pressure of the first solid hydrogen storage material.
Description
Technical Field
The invention relates to the technical field of hydrogen production, hydrogen purification, hydrogen storage, hydrogen pressurization and hydrogen production and hydrogenation integrated stations, in particular to a hydrogen production, hydrogen storage and hydrogenation integrated system and method.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The development and utilization of hydrogen energy are one of important ways for guaranteeing national energy safety and realizing low-carbon transformation. The hydrogen energy industry chain mainly comprises a plurality of links of hydrogen preparation, storage, transportation, addition and use. At present, a typical hydrogen adding station in China is mainly an off-site hydrogen supplying hydrogen adding station, hydrogen is transported to the hydrogen adding station through a long pipe trailer, pressurized by a hydrogen compressor and stored in a high-pressure storage tank in the station, and then hydrogen is added into a fuel cell automobile through a hydrogen adding machine. The hydrogenation stations have the problems of high hydrogen cost, high equipment investment cost, high maintenance cost, high safety risk of high-pressure gas hydrogen storage and the like.
The existing hydrogen adding station is to boost the pressure of hydrogen through compressor equipment, the cost of the compressor equipment accounts for about 30% of the total investment cost of the hydrogen adding station, the maintenance cost of the compressor equipment accounts for about 20% of the operation cost of the hydrogen adding station, and the safety accident hydrogen leakage is related to the compressor. Meanwhile, the high-pressure gaseous hydrogen storage in the station has high safety risk, and along with the continuous development of the hydrogen adding station, the hydrogen adding station technology with high safety and low cost is urgently needed.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a hydrogen production, hydrogen storage and hydrogenation integrated system and method.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a hydrogen production, hydrogen storage and hydrogenation integrated system, comprising a hydrogen production unit, a hydrogen purification storage unit, a hydrogen pressurizing unit and a hydrogenation device which are sequentially connected, wherein,
the hydrogen production unit comprises a skid-mounted natural gas hydrogen production device, a desulfurizing device and a CO conversion device which are connected in sequence;
the hydrogen purification storage unit comprises a heat exchanger, a metal hydride purification device and a first adjustable cold and heat source, wherein the metal hydride purification device is filled with a first solid hydrogen storage material which is arranged in the heat exchanger; the first adjustable cold and heat source is connected with the heat exchanger;
the hydrogen pressurizing unit comprises a second adjustable cold and heat source, a heat exchange device and a metal hydride compressor, wherein a second solid hydrogen storage material is filled in the metal hydride compressor, the second adjustable cold and heat source is connected with the heat exchange device, and the hydrogenation device is connected with the hydrogen pressurizing unit;
the hydrogen releasing platform pressure of the first solid hydrogen storage material is higher than the hydrogen absorbing platform pressure of the second solid hydrogen storage material, and the hydrogen releasing platform pressure of the second solid hydrogen storage material is higher than the hydrogen releasing platform pressure of the first solid hydrogen storage material.
According to the invention, the skid-mounted natural gas reforming hydrogen production process is selected to produce hydrogen on site in the hydrogen station, so that the hydrogen production and transportation cost can be effectively reduced. The inventor finds that the purity of the reformed gas is difficult to meet the requirement even after desulfurization and CO conversion by adopting the hydrogen production mode, so that the reformed gas needs to be purified to obtain pure hydrogen.
The existing hydrogenation station mainly adopts a high-pressure hydrogen storage tank to store hydrogen, has small volume hydrogen storage density and larger potential safety hazard, and is easy to leak and explode. The metal hydride purification device can store hydrogen in a solid metal hydrogen storage mode, so that the volume hydrogen storage density is improved, and the safety and operability can be effectively improved.
In addition, when the hydrogen in the solid hydrogen storage material is required to be released, the medium temperature of the first adjustable cold and heat source is adjusted, the solid hydrogen storage material is heated to the set temperature through the first heat exchanger, the hydrogen is released, the hydrogen is pressurized, the release pressure of the hydrogen is adjusted, the hydrogen with different pressures is provided, and the safety is higher, and the energy consumption is lower.
Because traditional hydrogen pressure boosting is generally mechanical pressure boosting, investment cost of compression equipment is high, energy consumption is high in the hydrogen pressure boosting process, the pressure of a hydrogen releasing platform of a first solid hydrogen storage material is higher than that of a hydrogen absorbing platform of a second solid hydrogen storage material, hydrogen released by the first solid hydrogen storage material can be absorbed and stored by the second solid hydrogen storage material, and when the hydrogen is required to be released, the pressure of the hydrogen can be adjusted by adjusting the temperature of the second solid hydrogen storage material, so that the gradual pressure boosting of the hydrogen can be realized. The hydrogen boosting mode can effectively reduce equipment investment cost and energy consumption, and has good safety.
The first solid hydrogen storage material not only can play a role in hydrogen purification and hydrogen storage, but also can be matched with the hydrogen pressurizing unit to realize gradual pressurization of hydrogen.
In some embodiments, the first solid state hydrogen storage material is La 0.4 Ce 0.4 Ca 0.2 Ni 5 Alloy, second solid hydrogen storage material is (Ti 0.97 Zr 0.03 ) 1.1 Cr 1.6 Mn 0.4 Or ZrFe 1.8 Ni 0.2 And (3) alloy.
A hydrogen purification storage unit is arranged, and a first solid hydrogen storage material La is filled in the metal hydride purification device 0.4 Ce 0.4 Ca 0.2 Ni 5 The alloy can selectively adsorb hydrogen, is convenient for discharging non-hydrogen impurities in reformed gas, and plays a good role in purifying hydrogen.
The solid hydrogen storage material selected by the invention can perform hydrogen absorption reaction at the same temperature, ensures that hydrogen discharge reaction occurs at the same temperature as far as possible, achieves the corresponding required platform pressure, can fully utilize the heat released by the adjacent metal hydride devices, and achieves the purposes of energy saving and consumption reduction.
The system is used for hydrogenation in a hydrogenation station, the hydrogen filling of 35MPa and 70MPa is required to be met, the existing hydrogen storage material is generally filled only aiming at a high-pressure gas cylinder, only one operation pressure can be realized during operation, the requirement of the gas station is difficult to meet, and when the solid hydrogen storage material is selected from (Ti 0.97 Zr 0.03 ) 1.1 Cr 1.6 Mn 0.4 Or ZrFe 1.8 Ni 0.2 When in alloy, the hydrogen filling requirement can be met more easily.
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 independent heat exchangers are arranged on the outer sides of each metal hydride purification device. The number of the metal hydride purifying devices is more than 2, so that the partial purifying devices can purify hydrogen, the partial purifying devices can carry out pressurized release of hydrogen, and the continuous operation of hydrogen purification, storage and release can be ensured.
An independent heat exchanger is arranged on the outer side of each metal hydride purification device, so that the temperature of each metal hydride purification device can be independently regulated, and the proper hydrogen storage purification temperature and the proper hydrogen release temperature are ensured.
Preferably, the number of metal hydride purification units is even. The partial purifiers are subjected to hydrogen absorption reaction, the other purifiers are subjected to hydrogen discharge reaction, then in the next time period, the former is subjected to hydrogen discharge reaction, and the latter is subjected to hydrogen absorption reaction, and the processes are repeated circularly, so that the continuous purification treatment of the impurity-containing hydrogen is realized.
Preferably, hydrogen storage alloys of the same hydrogen absorption and desorption pressure level are contained in different metal hydride purifiers.
Preferably, the hydrogen pressurizing unit comprises a two-stage pressurizing unit in series, and in the first-stage pressurizing unit, a metal hydride compressor is filled (Ti 0.97 Zr 0.03 ) 1.1 Cr 1.6 Mn 0.4 An alloy; zrFe filled in metal hydride compressor in second stage pressurizing unit 18 Ni 02 And (3) alloy.
As the hydrogen filling station needs to realize the filling of hydrogen at the pressure of 35MPa and 70MPa, experiments show 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 When the alloy is prepared, 35MPa hydrogen can be obtained when the temperature is regulated to release hydrogen. When 70MPa hydrogen is needed, part of 35MPa hydrogen can be subjected to secondary pressurization by utilizing a secondary pressurization unit, and ZrFe is filled in the secondary pressurization unit 1.8 Ni 0.2 When in alloy, 70MPa of hydrogen can be obtained.
The three hydrogen storage alloys adopted in the invention can be mutually connected in series according to reasonable platform pressure, so that the pressure of the hydrogen absorption platform of the next stage is lower than that of the hydrogen discharge platform of the previous stage, and the multi-stage supercharging effect can be achieved, thereby realizing the hydrogen filling of 35MPa and 70MPa.
It is further preferred that different metal hydride compressors are charged with hydrogen storage alloys of different hydrogen absorption and desorption pressure levels.
Further preferably, a buffer tank is connected between the first stage pressurizing unit and the second stage pressurizing unit.
Under the action of a second adjustable cold and heat source, hydrogen is subjected to hydrogen absorption reaction in a first-stage metal hydride compressor, the reaction temperature of the first-stage metal hydride compressor is set according to the hydrogenation pressure requirement, hydrogen release reaction is carried out under the action of the second adjustable cold and heat source, so that the compression of the hydrogen is realized, when 35MPa hydrogen is filled, medium-pressure hydrogen is output to a 35MPa hydrogenation device for hydrogen filling, when 70MPa hydrogen is filled, medium-pressure hydrogen is output to a buffer tank, when a hydrogenation station needs to simultaneously fill 35MPa and 70MPa hydrogen, the medium-pressure hydrogen can be output to the 35MPa hydrogenation device, and meanwhile, partial medium-pressure hydrogen is output to the buffer tank in a split mode;
and medium-pressure hydrogen in the buffer tank is introduced into the secondary metal hydride compressor, a hydrogen absorption reaction is carried out on the secondary metal hydride compressor under the action of a second external adjustable cold and heat source, then the reaction temperature of the secondary metal hydride compressor is set according to the hydrogenation pressure requirement, a hydrogen discharge reaction is carried out under the action of the second adjustable cold and heat source, and high-pressure hydrogen is output to a 70MPa hydrogenation device for hydrogen filling.
In some embodiments, the heat transfer medium of the first and second adjustable cold and heat sources is water or heat transfer oil.
The system also comprises connecting pipelines, valves and equipment control systems among the equipment, so that the automatic control and operation monitoring of the hydrogenation process are realized, and the operation safety of the hydrogenation system is ensured. And the pipelines connected between the devices of the system are respectively provided with an automatic control valve and a one-way valve, so that the reverse flow of gas is avoided.
In a second aspect, the present invention provides a hydrogen production, storage and hydrogenation integrated process comprising the steps of:
the hydrogen produced by desulfurization and CO conversion treatment is introduced into a metal hydride purifier by utilizing a skid-mounted natural gas reforming hydrogen production device, and hydrogen absorption reaction is carried out under the action of a first adjustable cold and heat source to generate metal hydride for storage and impurity gas discharge;
hydrogen stored in the metal hydride purifier is subjected to a hydrogen release reaction under the heating action of a first adjustable cold and hot source, and the generated hydrogen is introduced into a metal hydride compressor;
under the action of a second adjustable cold and heat source, hydrogen is subjected to hydrogen absorption reaction in the metal hydride compressor, the reaction temperature of the metal hydride compressor is set according to the hydrogenation pressure requirement, hydrogen discharge reaction is carried out, and the pressurization of the hydrogen is realized.
In some embodiments, when medium pressure hydrogen filling is performed, outputting medium pressure hydrogen to the medium pressure hydrogenation device for hydrogen filling;
preferably, when high-pressure hydrogen is filled, medium-pressure hydrogen is output to the buffer tank, the medium-pressure hydrogen in the buffer tank is introduced into the secondary metal hydride compressor to perform hydrogen absorption reaction, then the reaction temperature of the secondary metal hydride compressor is set according to the hydrogenation pressure requirement to perform hydrogen discharge reaction, and high-pressure hydrogen is output.
Preferably, when medium-pressure hydrogen and high-pressure hydrogen are required to be filled simultaneously, outputting the medium-pressure hydrogen to a medium-pressure hydrogenation device for medium-pressure hydrogenation, and meanwhile, splitting and outputting part of the medium-pressure hydrogen to a buffer tank, introducing the medium-pressure hydrogen in the buffer tank into a secondary metal hydride compressor for hydrogen absorption reaction, then, adjusting the reaction temperature of the secondary metal hydride compressor according to the hydrogenation pressure requirement, performing hydrogen discharge reaction, and outputting high-pressure hydrogen.
In the hydrogenation station, the medium-pressure hydrogen pressure is generally 35MPa, and the high-pressure hydrogen pressure is generally 70MPa.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
the skid-mounted natural gas reforming hydrogen production process is utilized to produce hydrogen on site, so that the production and transportation cost of hydrogen can be reduced, and the metal hydride is utilized to realize the purification, storage and pressurization of hydrogen.
The invention utilizes the heat management system and the adjustable cold and heat source in the system to realize the recycling of the heat release amount of the solid hydrogen storage material during the hydrogen absorption, and reduces the heating energy consumption required during the hydrogen release.
The invention utilizes the characteristic of selective absorption of the solid hydrogen storage material to hydrogen, can realize purification and impurity removal of hydrogen produced by a hydrogen production unit, can continuously release high-purity hydrogen products by the metal hydride purification device, meets the use requirement, can reduce the use of large purification equipment, and has the advantages of simple operation, low material cost, relatively simple equipment and process, reliable work, reduced occupied area, high purity and the like.
Compared with the traditional mechanical hydrogen compressor, the metal hydride compressor has the advantages of safety, environmental protection, no vibration and noise, good sealing performance, no friction, capability of effectively purifying hydrogen, low maintenance cost and the like, and also solves the problems of insufficient reliability and poor safety of the traditional mechanical boosting mode.
In addition, the existing hydrogenation station mainly adopts a high-pressure hydrogen storage tank as an in-station hydrogen storage container, has small volume hydrogen storage density and large potential safety hazard, and is easy to leak and explode. The invention stores the prepared hydrogen in a solid metal hydrogen storage mode, thereby not only improving the volume hydrogen storage density, but also improving the safety and operability of the equipment.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a schematic diagram of a three-stage metal hydride compression process in accordance with an embodiment of the present invention;
in the figure, P L Is at low temperature T L Pressing a lower hydrogen absorption platform; p (P) H Is at a high temperature T H Pressing a lower hydrogen discharging platform;
FIG. 2 is a schematic diagram of an integrated hydrogen production, storage and hydrogenation system in accordance with an embodiment of the present invention;
FIG. 3 is a schematic flow chart of an integrated hydrogen production, storage and hydrogenation process in accordance with an embodiment of the present invention.
In the figure, a 1-hydrogen production unit, a 2-first heat exchanger, a 3-first metal hydride purifier, a 4-second heat exchanger, a 5-second metal hydride purifier, a 6-first adjustable cold and heat source, a 7-first heat exchange device, an 8-primary metal hydride compressor, a 9-buffer tank, a 10-second heat exchange device, an 11-secondary metal hydride compressor, a 12-second adjustable cold and heat source, a 13-35MPa hydrogenation device and a 14-70MPa hydrogenation device are shown.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention is further illustrated below with reference to examples.
As shown in FIG. 1, the principle of the three-stage metal hydride compression process is that at a temperature T L When the input hydrogen pressure is larger than the platform pressure, the alloy starts to absorb hydrogen; then, the temperature of the hydrogen storage alloy is raised to T by means of a heating medium H At this time, the hydrogen pressure of the cavity is far lower than the hydrogen pressure of the hydrogen release platform, and the alloy can release hydrogen until the output hydrogen pressure reaches the hydrogen release platform pressure. Several hydrogen storage alloys with mutually matched platform pressures are mutually connected in series, so that the pressure of the hydrogen absorption platform of the next stage is lower than that of the hydrogen discharge platform of the previous stage, and the multi-stage supercharging effect can be achieved. The three hydrogen storage alloys adopted in the invention can be mutually connected in series according to reasonable platform pressure, so that the pressure of the hydrogen absorption platform of the next stage is lower than that of the hydrogen discharge platform of the previous stage, and the multi-stage supercharging effect can be achieved, thereby realizing the hydrogen filling of 35MPa and 70MPa.
As shown in fig. 2, according to one aspect of the present invention, there is provided a hydrogen production, storage and hydrogenation integrated system, the system comprising: a hydrogen production unit 1, a metal hydride purification device, a metal hydride compression device, a 35MPa hydrogenation device 13 and a 70MPa hydrogenation device 14;
wherein 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 and heat source 6;
wherein the metal hydride compression device comprises: the heat exchanger 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 and heat source 12.
The outlet of the hydrogen production unit 1 is connected with 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 with the inlet of the first-stage metal hydride compressor 8; the outlet of the primary metal hydride compressor 8 is respectively connected with the inlet of the buffer tank 9 and the inlet of the 35MPa hydrogenation device 13; the outlet of the buffer tank 9 is connected with the inlet of the secondary metal hydride 11; the outlet of the secondary metal hydride 11 is connected with the inlet of the 70MPa hydrogenation unit 14.
A thermal management system is arranged between two adjacent metal hydride devices and comprises a heat exchanger, an adjustable cold and heat source and a temperature control system. The thermal management system is used for storing heat released when the metal hydride device releases hydrogen and providing heat when the adjacent metal hydride device stores hydrogen.
In an alternative embodiment, the heat transfer medium between the thermal management system and each metal hydride device is water or heat transfer oil, but is not limited to these two heat transfer mediums, so long as cold/heat transfer between the thermal management system and the metal solid state hydrogen storage device is enabled.
The first metal hydride purifier 3 and the second metal hydride purifier 5 are internally provided with hydrogen storage alloys with the same hydrogen absorption and desorption pressure level, and the primary metal hydride compressor 8 and the secondary metal hydride compressor 11 are internally provided with hydrogen storage alloys with different hydrogen absorption and desorption pressure levels and are different from the hydrogen storage alloys in the metal hydride purifiers. By adopting different solid hydrogen storage alloys, the hydrogen release temperature in the metal hydride device is controlled to be different, so that the hydrogen release pressure is controlled to be different, and the final hydrogen filling requirements of 35MPa and more than 70MPa are realized.
La is adopted as a solid hydrogen storage material in the metal hydride purifier 0.4 Ce 0.4 Ca 0.2 Ni 5 Alloy, solid hydrogen storage material in the primary metal hydride compressor adopts (Ti 0.97 Zr 0.03 ) 1.1 Cr 1.6 Mn 0.4 Alloy, wherein ZrFe is adopted as solid hydrogen storage material of the secondary metal hydride compressor 1.8 Ni 0.2 And (3) alloy. The invention relates to a solidThe solid hydrogen storage material is not limited to the above materials, and can be matched with the solid hydrogen storage material to realize gradual pressure increase of hydrogen;
wherein the pressure of the hydrogen at the outlet of the hydrogen production unit is 1.5-2.5MPa; the low-pressure hydrogen absorption temperature in the first metal hydride purifier and the second metal hydride purifier is 20 ℃, the pressure is 1.0MPa, the high-pressure hydrogen release temperature is 90 ℃, and the pressure is 9.2MPa; the low-pressure hydrogen absorption temperature in the primary metal hydride compressor is 20 ℃, the pressure is 6.9MPa, the high-pressure hydrogen release temperature is 90 ℃, and the pressure is 43.6MPa; the low-pressure hydrogen absorption temperature in the secondary metal hydride compressor is 20 ℃, the pressure is 26.3MPa, the high-pressure hydrogen release temperature is 68 ℃, and the pressure is 90.6MPa.
The hydrogen production mode adopted by the hydrogen production unit 1 is that the skid-mounted natural gas reforming hydrogen production device carries out hydrogen production in the hydrogen addition station, and the hydrogen production in the hydrogen addition station can not only save the cost generated by expensive hydrogen transportation links, but also greatly reduce the hydrogen cost. The hydrogen production process in the hydrogen production unit 1 comprises a pre-desulfurization treatment and a post-CO conversion procedure, so that the service life and the performance of a subsequent metal hydride device can be ensured.
In an alternative embodiment, the 35MPa hydrogenation device 13 of the present invention includes at least one hydrogenation machine, and the 70MPa hydrogenation device 14 includes at least one hydrogenation machine, and a hydrogenation gun is disposed in the hydrogenation machine to implement hydrogen filling.
Besides the main equipment, the system also comprises connecting pipelines, valves and equipment control systems among the equipment, so that the automatic control and operation monitoring of the hydrogenation process are realized, and the operation safety of the hydrogenation system is ensured.
An integrated method for producing hydrogen, storing hydrogen and hydrogenating, which comprises the following steps:
the hydrogen is prepared by the hydrogen preparing unit 1 by utilizing a natural gas reforming hydrogen preparing device, the gas before reaction is required to be subjected to desulfurization treatment, and the reformed gas enters a metal hydride purifying device after CO conversion;
the prepared hydrogen is introduced into a metal hydride purification device, the first metal hydride purifier 3 (or the second metal hydride purifier 5) is subjected to hydrogen absorption reaction under the action of the first adjustable cold and heat source 6, the hydrogen is stored, the impurity tail gas after the reaction is discharged out of the system, the metal hydride in the second metal hydride purifier 5 (or the first metal hydride purifier 3) is subjected to hydrogen discharge reaction under the action of the first adjustable cold and heat source 6, high-purity hydrogen with the purity of 99.999% can be generated, and the primary pressurization is realized;
by arranging a plurality of metal hydride purifiers, hydrogen absorption and hydrogen discharge reactions in different metal hydride purifiers alternately and circularly reciprocate, so that the continuous purification treatment of the impurity-containing hydrogen is realized; after the gas passes through the metal hydride purifier, two functions of gas purification and gas pressurization are realized simultaneously;
the purified high-purity hydrogen is introduced into a primary metal hydride compressor 8, a hydrogen absorption reaction occurs under the action of a second adjustable cold and heat source 12, the reaction temperature of the primary metal hydride compressor 8 is set according to the downstream hydrogen utilization pressure requirement, a hydrogen discharge reaction occurs under the action of the second adjustable cold and heat source 12, the compression of the hydrogen is realized, and medium-pressure hydrogen is output to a 35MPa hydrogenation device 13 to fill a fuel cell vehicle through a hydrogenation machine or is introduced into a medium-pressure hydrogen buffer tank 9;
the medium-pressure hydrogen enters a secondary metal hydride compressor 11 through a buffer tank 9, a hydrogen absorption reaction occurs under the action of a second adjustable cold and heat source 12, the reaction temperature of the secondary metal hydride compressor 11 is set according to the downstream hydrogen utilization pressure requirement, a hydrogen release reaction occurs under the action of the second adjustable cold and heat source 12, the hydrogen is further compressed, and high-pressure hydrogen is output to a 70MPa hydrogenation device 14;
the high-pressure hydrogen enters a 70MPa hydrogenation device 14, and the fuel cell vehicle is filled through a hydrogenation machine.
In the method, the pipelines between the devices are respectively provided with the valve and the automatic control system, so that the control and the safety guarantee of the working state of the system are realized.
According to the method, the metal hydride is used as a medium, the characteristics of PCT characteristic curve of the hydrogen storage material and selective absorption of hydrogen are utilized to realize the purification of high-purity hydrogen from the natural gas reformed gas, the high-purity hydrogen is stored in the metal hydride stably, the hydrogen production purification device and the subsequent hydrogen storage device are concentrated into one set of device, the occupied area and the investment cost are saved, meanwhile, the metal hydride has the hydrogen compression function, the hydrogenation of 35MPa and 70MPa can be realized in the same hydrogenation station at the same time, and the problems of safe hydrogen storage, safe hydrogen pressurization, large occupied area of the hydrogenation station and over-high investment cost at present are solved.
The invention can be used for the construction of the hydrogenation station, and by reasonably configuring each device through the coupling calculation of the filling scale of the hydrogenation station, the hydrogen production by reforming the natural gas and the metal solid hydrogen storage and the calculation of the cold and heat energy, 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.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides a hydrogen production, hydrogen storage and hydrogenation integration system which characterized in that: comprises a hydrogen production unit, a hydrogen purification storage unit, a hydrogen pressurizing unit and a hydrogenation device which are connected in sequence,
the hydrogen production unit comprises a skid-mounted natural gas hydrogen production device, a desulfurizing device and a CO conversion device which are connected in sequence;
the hydrogen purification storage unit comprises a heat exchanger, a metal hydride purification device and a first adjustable cold and heat source, wherein the metal hydride purification device is filled with a first solid hydrogen storage material which is arranged in the heat exchanger; the first adjustable cold and heat source is connected with the heat exchanger;
the hydrogen pressurizing unit comprises a second adjustable cold and heat source, a heat exchange device and a metal hydride compressor, wherein a second solid hydrogen storage material is filled in the metal hydride compressor, the second adjustable cold and heat source is connected with the heat exchange device, and the hydrogenation device is connected with the hydrogen pressurizing unit;
the hydrogen releasing platform pressure of the first solid hydrogen storage material is higher than the hydrogen absorbing platform pressure of the second solid hydrogen storage material, and the hydrogen releasing platform pressure of the second solid hydrogen storage material is higher than the hydrogen releasing platform pressure of the first solid hydrogen storage material.
2. The integrated hydrogen production, storage and hydrogenation system of claim 1, wherein: the first solid hydrogen storage material is La 0.4 Ce 0.4 Ca 0.2 Ni 5 Alloy, second solid hydrogen storage material is (Ti 0.97 Zr 0.03 ) 1.1 Cr 1.6 Mn 0.4 Or ZrFe 1.8 Ni 0.2 And (3) alloy.
3. The integrated hydrogen production, storage and hydrogenation system of claim 1, wherein: the number of the metal hydride purifying devices in the hydrogen purifying and storing unit is more than 2, the metal hydride purifying devices are connected in parallel, and independent heat exchangers are arranged on the outer sides of the metal hydride purifying devices.
4. The integrated hydrogen production, storage and hydrogenation system of claim 3 wherein: the number of metal hydride purification units is even.
5. The integrated hydrogen production, storage and hydrogenation system of claim 3 wherein: hydrogen storage alloys with the same hydrogen absorption and desorption pressure levels are filled in different metal hydride purifiers.
6. The integrated hydrogen production, storage and hydrogenation system of claim 2, wherein: the hydrogen pressurizing unit includes two-stage pressurizing units in series, and 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 An alloy; zrFe filled in metal hydride compressor in second stage pressurizing unit 1.8 Ni 0.2 And (3) alloy.
7. The integrated hydrogen production, storage and hydrogenation system of claim 6 wherein: hydrogen storage alloys with different hydrogen absorption and desorption pressure grades are filled in different metal hydride compressors;
preferably, a buffer tank is connected between the first stage pressurizing unit and the second stage pressurizing unit.
8. The integrated hydrogen production, storage and hydrogenation system of claim 1, wherein: the heat conduction medium of the first adjustable cold and heat source and the second adjustable cold and heat source is water or heat conduction oil.
9. An integrated method for producing hydrogen, storing hydrogen and hydrogenating, which is characterized in that: the method comprises the following steps:
the hydrogen produced by desulfurization and CO conversion treatment is introduced into a metal hydride purifier by utilizing a skid-mounted natural gas reforming hydrogen production device, and hydrogen absorption reaction is carried out under the action of a first adjustable cold and heat source to generate metal hydride for storage and impurity gas discharge;
hydrogen stored in the metal hydride purifier is subjected to a hydrogen release reaction under the heating action of a first adjustable cold and hot source, and the generated hydrogen is introduced into a metal hydride compressor;
under the action of a second adjustable cold and heat source, hydrogen is subjected to hydrogen absorption reaction in the metal hydride compressor, the reaction temperature of the metal hydride compressor is set according to the hydrogenation pressure requirement, hydrogen discharge reaction is carried out, and the pressurization of the hydrogen is realized.
10. The integrated hydrogen production, storage and hydrogenation process of claim 9, wherein: when medium-pressure hydrogen filling is carried out, outputting medium-pressure hydrogen to a medium-pressure hydrogenation device for hydrogen filling;
preferably, when high-pressure hydrogen is filled, 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 perform hydrogen absorption reaction, then the reaction temperature of the secondary metal hydride compressor is set according to the hydrogenation pressure requirement to perform hydrogen release reaction, and high-pressure hydrogen is output;
preferably, when medium-pressure hydrogen and high-pressure hydrogen are filled simultaneously, medium-pressure hydrogen is output to a medium-pressure hydrogenation device for medium-pressure hydrogenation, partial medium-pressure hydrogen is output to a buffer tank in a split mode, the medium-pressure hydrogen in the buffer tank is introduced into a secondary metal hydride compressor for hydrogen absorption reaction, then the reaction temperature of the secondary metal hydride compressor is adjusted according to the hydrogenation pressure requirement for hydrogen discharge reaction, and high-pressure hydrogen is output.
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