CN111075524A - Metal hydride ultralow temperature circulating work-doing system - Google Patents
Metal hydride ultralow temperature circulating work-doing system Download PDFInfo
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- CN111075524A CN111075524A CN201911369485.0A CN201911369485A CN111075524A CN 111075524 A CN111075524 A CN 111075524A CN 201911369485 A CN201911369485 A CN 201911369485A CN 111075524 A CN111075524 A CN 111075524A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
- F01K25/08—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
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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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K27/00—Plants for converting heat or fluid energy into mechanical energy, not otherwise provided for
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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
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Abstract
The invention relates to a metal hydride ultralow temperature circulating work doing system which comprises a protective cover, a B1 metal hydrogen storage material reaction bed, a B2 metal hydrogen storage material reaction bed, a hydrogen heat exchanger, a heat exchanger, an air heat exchanger, a hydrogen expander and a liquid hydrogen high-pressure pump, wherein the B1 metal hydrogen storage material reaction bed, the B2 metal hydrogen storage material reaction bed, the hydrogen heat exchanger, the air heat exchanger, the hydrogen. The B1 metal hydrogen storage material reaction bed and the B2 metal hydrogen storage material reaction bed are respectively connected with a hydrogen expander through the shell side of a hydrogen heat exchanger and an air heat exchanger, and then return to the B1 metal hydrogen storage material reaction bed and the B2 metal hydrogen storage material reaction bed through the tube side of the hydrogen heat exchanger and the heat exchanger. The present invention utilizes the hydrogen absorbing/releasing characteristic of metal hydride to drive the expander to do work.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of energy, and relates to a metal hydride ultralow-temperature circulating work-doing system.
Background
Energy shortage, environmental pollution, global climate change, and the development of clean, efficient, safe and sustainable energy is urgently needed, wherein hydrogen energy is being valued by more and more countries. The engine industry has developed rapidly into the twenty-first century, however, gasoline and diesel engines remain the major engine choices. Gasoline and diesel oil are non-renewable resources, in order to alleviate a series of negative effects caused by the shortage of petroleum resources and reduce atmospheric pollution and exhaust emission of engines, alternative fuels of engines need to be found, and hydrogen energy is the most ideal clean fuel at present. With the stricter environmental protection measures in various countries in the world, hydrogen energy engines have become a key point in engine research and development due to the characteristics of energy conservation, low emission and the like, and have already begun to be commercialized. The traditional hydrogen energy utilization mostly obtains heat energy and kinetic energy through directly burning gaseous hydrogen, but gaseous hydrogen is difficult for storage and transportation, and the obtained hydrogen energy of burning directly can produce a series of influences problems of safe handling such as knockings, unstability on power system.
Disclosure of Invention
The invention aims to provide a metal hydride ultralow-temperature circulating work system, which takes hydrogen as a circulating working medium, utilizes the characteristics of hydrogen absorption, heat release and hydrogen release of a metal hydrogen storage material, applies work through an expansion machine, drives work equipment to work or drives power generation equipment to generate power, fully utilizes natural energy and industrial waste heat, is beneficial to energy conservation and emission reduction and creates economic benefits.
The embodiment of the application provides a metal hydride ultralow temperature cycle work system, including the safety cover to and set up B1 metal hydrogen storage material reaction bed, B2 metal hydrogen storage material reaction bed, hydrogen heat exchanger, air heat exchanger, hydrogen expander and liquid hydrogen high-pressure pump in the safety cover.
The first hydrogen discharge outlet of the B1 metal hydrogen storage material reaction bed and the second hydrogen discharge outlet of the B2 metal hydrogen storage material reaction bed are respectively connected with the inlet of a liquid hydrogen high-pressure pump, the outlet of the liquid hydrogen high-pressure pump is connected with the shell side inlet of a heat exchanger, and the shell side outlet of the heat exchanger is respectively connected with the first hydrogen absorption inlet of the B1 metal hydrogen storage material reaction bed and the second hydrogen absorption inlet of the B2 metal hydrogen storage material reaction bed.
A first heat exchange outlet of the B1 metal hydrogen storage material reaction bed and a second heat exchange outlet of the B2 metal hydrogen storage material reaction bed are respectively connected with a shell pass inlet of a hydrogen heat exchanger, a shell pass outlet of the hydrogen heat exchanger is connected with a shell pass inlet of an air heat exchanger, a shell pass outlet of the air heat exchanger is connected with an inlet of a hydrogen expander, a primary expansion outlet of the hydrogen expander is connected with a tube pass inlet of the hydrogen heat exchanger, a tube pass outlet of the hydrogen heat exchanger is connected with a secondary expansion inlet of the hydrogen expander, a secondary expansion outlet of the hydrogen expander is connected with a tube pass inlet of the heat exchanger, and a tube pass outlet of the heat exchanger is connected with a first liquefaction inlet of the B1 metal hydrogen storage material reaction bed and a second liquefaction inlet of the B2 metal hydrogen storage material reaction bed.
Be provided with nitrogen gas heat transfer coil and air heat transfer coil in the air heat exchanger, nitrogen gas heat transfer coil's tube side entry and tube side export all set up in the guard shield, and air heat transfer coil's tube side entry and tube side export all set up outside the guard shield.
The B1 metal hydrogen storage material reaction bed and the B2 metal hydrogen storage material reaction bed are both provided with internal circulation bypasses, the internal circulation bypasses are provided with hydrogen medium internal circulation pumps, and when the metal hydrogen storage material reaction bed performs hydrogen absorption and hydrogen desorption operations, the circulation reciprocation of hydrogen medium in the B1 metal hydrogen storage material reaction bed and the B2 metal hydrogen storage material reaction bed is realized, so that the operation working condition is stabilized.
Further, the system also includes a generator. The hydrogen expander is coaxially connected with a generator, and a generator circuit is connected to an external power grid and/or a storage battery. Hydrogen expanders include, but are not limited to, rotary and piston-type work machines.
When the metal hydrogen storage material reaction bed working point β 2 of B2 absorbs hydrogen and releases heat, a part of the hydrogen entering the metal hydrogen storage material reaction bed of B2 is absorbed into metal hydride in the metal hydrogen storage material reaction bed of B2, the rest of the hydrogen is raised in temperature and flows out of the metal hydrogen storage material reaction bed of B2 to enter an air heat exchanger, the metal hydride is strictly limited in a grid in the metal hydrogen storage material reaction bed of B2, any metal hydride particles are not allowed to overflow out of the grid, the grid only allows hydrogen or liquid hydrogen to enter and exit, for the working point β of the metal hydrogen storage material reaction bed of B1, the hydrogen is only allowed to flow out of the metal hydrogen storage material reaction bed of B1, the metal hydride is strictly limited in a grid in the metal hydrogen storage material reaction bed of B1, only allows liquid hydrogen and a small amount of gaseous hydrogen to flow out of the metal hydrogen storage material reaction bed of B1, the metal hydrogen storage material reaction bed is strictly limited in a grid in the metal hydrogen storage material reaction bed of B1, only allows liquid hydrogen and a small amount of B1, and the metal hydrogen storage material reaction bed is changed into a reciprocating reaction material 369634, and the metal hydrogen storage material reaction bed is changed into a reciprocating working point 369685.
The B1 metal hydrogen storage material reaction bed and the B2 metal hydrogen storage material reaction bed are used for cooling and liquefying hydrogen entering from a hydrogen inlet and cooling and liquefying hydrogen released by the metal hydrogen storage material when hydrogen is released and absorbed at low temperature and low pressure. The B1 metal hydrogen storage material reaction bed and the B2 metal hydrogen storage material reaction bed are used for further heating treatment of part of hydrogen entering from the heat exchange inlet when absorbing hydrogen at high temperature and high pressure and releasing heat, and the other part of hydrogen enters the metal hydrogen storage material after absorbing hydrogen.
Furthermore, the metal hydride filled in the B1 metal hydrogen storage material reaction bed and the metal hydride filled in the B2 metal hydrogen storage material reaction bed are the same, the filling amount is allowed to be the same, the filling amount is also allowed to be different, the hydrogen absorption/desorption operation of the metal hydride and the metal hydride is realized by switching valves, and the switching frequency can be adjusted according to the process conditions. The amount of metal hydride filled in a single metal hydrogen storage material reaction bed allows redundancy, so that the hydrogen absorbing and releasing rate of each time can meet the requirement of rapid high-low pressure switching, and the redundant equivalent multiple can be adjusted according to the process conditions. A 1-fold redundant equivalent is the minimum amount of metallic hydrogen storage material required for a single hydrogen absorption saturation of the metallic hydrogen storage material throughout a complete process cycle. The metal hydride stored in the B1 metal hydrogen storage material reaction bed and the B2 metal hydrogen storage material reaction bed can be any combination of any particle size, and at the same time, the metal hydride can be solid or hollow.
Further, the safety cover is provided with a combustible gas alarm and a protective gas inlet, the protective gas inlet is provided with a valve, and gas filled in the safety cover comprises but is not limited to hydrogen, nitrogen and helium.
Further, besides using gaseous hydrogen as the circulating heat exchange medium of the work-doing system, other gases can be used as the circulating heat exchange medium. In addition, other substances including but not limited to stable solids, liquids, or liquid organic hydrides can be used instead of hydrogen as the circulating heat exchange medium of the work-producing system. The heat exchange mode can be direct heat exchange or partition wall heat exchange, and the heat exchange medium for partition wall heat exchange can be gas, liquid, solid or mixture of the above or mixture of every two.
The metal hydride work including but not limited to positive temperature correlation is defined as absorbing high-pressure hydrogen at high temperature to release high-temperature heat and releasing low-pressure hydrogen at low temperature to release low-temperature cold. Absorbing hydrogen to release high-temperature heat at high temperature, and utilizing the metal hydrogen storage material reaction bed to directly exchange heat to heat the working hydrogen. The system has at least one negative pressure unit, which is either the negative pressure of metal hydride, the negative pressure of hydrogen liquefaction, or the combination of the above negative pressures. The heat exchange of the working hydrogen at low temperature is to utilize the heat absorption of the metal hydride when releasing low-pressure hydrogen at low temperature, and the low-temperature cold energy generated by the metal hydride is used for cooling the working hydrogen for liquefaction. The system equipment and the pipeline are provided with external heat preservation, internal heat preservation and internal and external heat preservation.
The high-temperature point β 2 of the metal hydride comprises but is not limited to any temperature lower than the ambient temperature, and the low-temperature point β 1 of the metal hydride comprises but is not limited to lower than the liquefaction temperature of hydrogen or comprises but is not limited to the vicinity of the liquefaction temperature of the hydrogen.
At least one point of the state of the metal hydride is allowed to be heated briefly within each cycle or at intervals of the cycle to restore the kinetic properties of the metal hydride, thereby accelerating the hydrogen absorption and desorption rate of the metal hydride. The parameters of the hydrogen absorption/desorption state point and the working point of the metal hydrogen storage material can be adjusted at will according to the process requirements. The system also allows the protective cover to be removed and the heat energy input to the system to be derived from the air heat exchanger.
The metal hydrogen storage material reaction beds can also be provided with three or more metal hydrogen storage material reaction beds, and can be operated in a switching mode of any combination such as 'two absorption and one release' (two reaction beds carry out hydrogen absorption operation and the other reaction bed carries out hydrogen release operation) or 'two absorption and release' and the like so as to adapt to the working condition of inconsistent hydrogen absorption/release reaction rates.
The work system disclosed by the invention is arranged on vehicles such as automobiles and ships, communication equipment such as mobile phones and the like or other equipment, can utilize energy carried by natural substances, and converts Kouleau hydrogen energy into mechanical energy or electric energy by working medium circulation work so as to drive the equipment to operate, thereby realizing green energy. The Kohlexpre hydrogen energy is defined to include, but is not limited to, energy from nature combined with similar systems of the present invention.
Further, the system also comprises a metal hydrogen storage material replacing device, and the metal hydrogen storage material replacing device is used for taking out and filling the metal hydrogen storage materials in the B1 metal hydrogen storage material reaction bed and the B2 metal hydrogen storage material reaction bed.
The metal hydrogen storage material replacing device comprises a separation tank, a recovery tank, a residual hydrogen absorbing unit, a vacuum tank, a protective gas compressor, a high-pressure protective gas tank, a raw material tank, a feeder, a drawing metering instrument, an adding metering instrument and a filling gun. The filling gun is provided with a sealing ring and a locking flange, the adding and extracting ports of the B1 metal hydrogen storage material reaction bed and the B2 metal hydrogen storage material reaction bed are provided with stop valves with coded locks, and the filling gun is hermetically connected with the adding and extracting port of the B1 metal hydrogen storage material reaction bed or the B2 metal hydrogen storage material reaction bed through the locking flange. The filling gun is provided with a feeding-discharging port, the feeding-discharging port is connected to a separating tank through an adding-pumping shared pipeline and a pumping pipeline, a solid outlet of the separating tank is connected to a recovery tank through a pumping meter, a gas outlet of the separating tank is connected to a vacuum tank through a residual hydrogen absorption unit, the vacuum tank is connected to a high-pressure protective gas tank through a one-way valve and a protective gas compressor, an outlet of the high-pressure protective gas tank is divided into two paths, one path is connected to a feeder, the other path is connected to a protective gas inlet of the filling gun through a protective gas pipeline, and a raw material tank is connected to the feeding-discharging port of the filling gun through the feeder, the adding meter, an adding pipeline. The purpose of using the metal hydrogen storage material replacing device to extract the metal hydrogen storage material includes, but is not limited to, replacing the metal hydrogen storage material to recover the hydrogen absorption and desorption performance thereof, or heating the metal hydrogen storage material to increase the hydrogen absorption and desorption kinetic performance thereof.
The invention discloses a metal hydride ultralow temperature circulating work-doing system, wherein metal hydrides are filled in a B1 metal hydrogen storage material reaction bed and a B2 metal hydrogen storage material reaction bed, the metal hydrides are cooled or heated to do work hydrogen by utilizing the characteristics of hydrogen absorption, heat release and hydrogen absorption of the metal hydrides, and work is done by a hydrogen expander to drive work-doing equipment to work or drive power generation equipment to generate power, so that the natural energy and industrial waste heat are fully utilized, the energy conservation and emission reduction are facilitated, and the economic benefit is created. The work system disclosed by the invention is arranged on vehicles such as ships and other equipment, can utilize energy carried by other natural substances, and can drive the expander to do work through working medium circulation, so that the Kouleapu hydrogen energy is converted into mechanical energy to drive the vehicles to run, and green traffic and power generation are realized. The metal hydride ultralow temperature circulating work system disclosed by the invention can absorb the heat of the gas filled in the protective cover and the heat of the environment outside the protective cover.
In addition, the metal hydride ultralow temperature circulating work-doing system disclosed by the invention realizes the circulating reciprocation of the hydrogen medium in the bed layer when the metal hydrogen storage material reaction bed performs hydrogen absorption and hydrogen desorption operations by arranging the internal circulating bypass on the metal hydrogen storage material reaction bed and arranging the hydrogen medium internal circulating pump on the internal circulating bypass, thereby stabilizing the operation working condition.
Drawings
Fig. 1 is a schematic structural diagram of a metal hydride ultralow temperature cycle work system provided in embodiment 1 of the present invention;
FIG. 2 is a view showing the operating state of a metal hydride according to example 1;
fig. 3 is a schematic structural view of a metal hydrogen storage material replacement device.
Wherein: 1-B1 metal hydrogen storage material reaction bed, 2-B2 metal hydrogen storage material reaction bed, 3-hydrogen heat exchanger, 4-nitrogen heat exchange coil, 5-air heat exchange coil, 6-metal hydrogen storage material replacing device, 7-hydrogen medium internal circulation pump, 14-air heat exchanger, 17-generator, 18-hydrogen expander, 19-liquid hydrogen high pressure pump, 21-first hydrogen discharge outlet, 22-first hydrogen absorption inlet, 23-first heat exchange outlet, 21 '-second hydrogen discharge outlet, 22' -second hydrogen absorption inlet, 23 '-second heat exchange outlet, 27-protective gas inlet, 28-protective cover, 29-combustible gas alarm, 30-valve, 32-first liquefied inlet, 32' -second liquefied inlet, 33-heat exchanger, 39-one-way valve, 111-filling gun, 114-separation tank, 115-recovery tank, 116-residual hydrogen absorption unit, 117-vacuum tank, 119-protective gas compressor, 120-high pressure protective gas tank, 121-protective gas pipeline, 122-extraction pipeline, 123-raw material tank, 124-feeder, 125-addition-extraction shared pipeline, 126-extraction metering instrument, 127-addition metering instrument, 128-addition pipeline.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings. The scope of protection of the invention is not limited to the embodiments, and any modification made by those skilled in the art within the scope defined by the claims also falls within the scope of protection of the invention.
The embodiment of the invention provides a metal hydride ultralow temperature cycle work-doing system, as shown in fig. 1, the system comprises a B1 metal hydrogen storage material reaction bed 1, a B2 metal hydrogen storage material reaction bed 2, a liquid hydrogen high-pressure pump 19, an air heat exchanger 14, a hydrogen expander 18 and a generator 17.
The B1 metallic hydrogen storage material reaction bed 1 is provided with a first hydrogen discharge outlet 21, a first heat exchange outlet 23, a first liquefaction inlet 32 and a first hydrogen absorption inlet 22. The B2 metallic hydrogen storage material reaction bed 2 is provided with a second hydrogen discharge outlet 21 ', a second heat exchange outlet 23', a second liquefaction inlet 32 'and a second hydrogen absorption inlet 22'.
The B1 metal hydrogen storage material reaction bed 1 and the B2 metal hydrogen storage material reaction bed 2 are both provided with an internal circulation bypass, and the internal circulation bypass is provided with a hydrogen medium internal circulation pump 7, so that when the metal hydrogen storage material reaction bed performs hydrogen absorption and hydrogen desorption operations, the hydrogen medium is used for circulating and reciprocating in the bed layer to stabilize the operation working condition. In addition, in order to stabilize the pressure, it is also conceivable to provide a hydrogen intermediate tank in the main hydrogen pipe before the high-pressure liquid hydrogen pump 19 and the hydrogen heat exchanger 3.
The first hydrogen discharge outlet 21 of the B1 metal hydrogen storage material reaction bed 1 and the second hydrogen discharge outlet 21 'of the B2 metal hydrogen storage material reaction bed 2 are respectively connected with the inlet of the liquid hydrogen high-pressure pump 19, the outlet of the liquid hydrogen high-pressure pump 19 is connected with the shell-side inlet of the heat exchanger 33, and the shell-side outlet of the heat exchanger 33 is respectively connected with the first hydrogen absorption inlet 22 of the B1 metal hydrogen storage material reaction bed 1 and the second hydrogen absorption inlet 22' of the B2 metal hydrogen storage material reaction bed 2.
The first heat exchange outlet 23 of the B1 metal hydrogen storage material reaction bed 1 and the second heat exchange outlet 23' of the B2 metal hydrogen storage material reaction bed 2 are respectively connected with the shell-side inlet of the hydrogen heat exchanger 3, the shell pass outlet of the hydrogen heat exchanger 3 is connected with the shell pass inlet of the air heat exchanger 14, the shell pass outlet of the air heat exchanger 14 is connected with the inlet of the hydrogen expander 18, the hydrogen expander 18 is an intermediate suction type expander, the primary expansion outlet of the hydrogen expander 18 is connected with the tube pass inlet of the hydrogen heat exchanger 3, the tube pass outlet of the hydrogen heat exchanger 3 is connected with the secondary expansion inlet of the hydrogen expander 18, the secondary expansion outlet of the hydrogen expander 18 is connected with the tube pass inlet of the heat exchanger 33, and the tube pass outlet of the heat exchanger 33 is connected with the first liquefaction inlet 32 of the B1 metal hydrogen storage material reaction bed 1 and the second liquefaction inlet 32' of the B2 metal hydrogen storage material reaction bed 2. The hydrogen expander 18 is coaxially connected with the generator 17, and the generator 17 is electrically connected with an external power grid and/or a storage battery; the hydrogen expander 18 may be replaced with, but is not limited to, a two-stage piston expander.
The B1 metal hydrogen storage material reaction bed 1 or the B2 metal hydrogen storage material reaction bed 2 is respectively connected with a metal hydrogen storage material replacing device 6 through an adding and extracting port, and the metal hydrogen storage material in the bed layer can be taken out and filled through the metal hydrogen storage material replacing device 6. The replacement frequency of the metal hydrogen storage material in the reaction bed can be set arbitrarily according to the actual needs of working conditions. As shown in FIG. 3, the metal hydrogen storage material replacing device 6 can safely and quickly convey the used metal hydrogen storage material in the reaction bed, and can also safely and quickly inject the granular or powdery metal hydrogen storage material into the reaction bed, and can also accurately and quickly measure the quantity. The metal hydrogen storage material replacing device 6 adopts a mechanical conveying, gas conveying or liquid conveying replacing mode, and can realize the purpose of accurately and safely conveying the metal hydrogen storage material into the reaction bed. The metal hydrogen storage material replacement device 6 includes a separation tank 114, a recovery tank 115, a residual hydrogen absorption unit 116, a vacuum tank 117, a shielding gas compressor 119, a high-pressure shielding gas tank 120, a raw material tank 123, a feeder 124, a drawing meter 126, an addition meter 127, and a filling gun 111. The filling gun is provided with a sealing ring and a locking flange, the adding and extracting ports of the B1 metal hydrogen storage material reaction bed 1 and the B2 metal hydrogen storage material reaction bed 2 are provided with stop valves with coded locks, and the filling gun 111 is hermetically connected with the adding and extracting port of the B1 metal hydrogen storage material reaction bed 1 or the B2 metal hydrogen storage material reaction bed 2 through the locking flange. The filling gun 111 is provided with a feed-discharge port connected to the separation tank 114 through an addition-suction common line 125 and a suction line 122, a solid outlet of the separation tank 114 is connected to a recovery tank 115 through a suction meter 126, a gas outlet of the separation tank 114 is connected to a vacuum tank 117 through a residual hydrogen absorption unit 116, and the vacuum tank 117 is connected to a high-pressure protection gas tank 120 through a check valve 39 and a protection gas compressor 119. The outlet of the high-pressure protective gas tank 120 is divided into two paths, one path is connected to the feeder 124, and the other path is connected to the protective gas inlet of the filling gun 111 through the protective gas pipeline 121. The material tank 123 is connected to a feed-discharge port of the filling gun 111 through a feeder 124, an addition meter 127, an addition line 128, and an addition-drawing common line 125. The purpose of using the metal hydrogen storage material replacement device 6 to extract the metal hydrogen storage material includes, but is not limited to, replacing the metal hydrogen storage material to recover the hydrogen absorption and desorption performance thereof, or heating the metal hydrogen storage material to increase the hydrogen absorption and desorption kinetic performance thereof.
The nitrogen heat exchange coil 4 at the upper part of the air heat exchanger 14 is connected with the internal environment of the protective cover 28, and the heat radiation Q1 of the equipment in the protective cover 28 is input into the air heat exchanger 14, so that the environment in the protective cover 28 is kept constant at-50 ℃; external heat energy Q2 is input into the air heat exchanger 14 through the air heat exchange coil 5 at the lower part of the air heat exchanger 14, so that the temperature of the hydrogen is increased by using the external heat energy Q2 to enhance the work capacity of the hydrogen, and the external heat energy Q2 can be air heat energy or heat energy including but not limited to a cold water refrigerating system, and cold energy is provided for the outside while the external heat energy is used. The system also allows for the removal of the protective cover 28 and the heat energy input to the system is all from the air heat exchanger 14.
The B1 metal hydrogen storage material reaction bed 1 and the B2 metal hydrogen storage material reaction bed 2 are used for cooling and liquefying hydrogen entering from a hydrogen inlet when hydrogen is discharged and absorbed at low temperature and low pressure, and cooling and liquefying hydrogen discharged from the metal hydrogen storage material, and the hydrogen discharged from the metal hydrogen storage material and the hydrogen cooled by entering the reaction bed can be liquid or gas when the hydrogen is discharged from the reaction bed and then is cooled and liquefied outside the reaction bed. The B1 metal hydrogen storage material reaction bed 1 and the B2 metal hydrogen storage material reaction bed 2 are used for further heating treatment of a part of hydrogen entering from the heat exchange inlet when absorbing hydrogen at high temperature and high pressure and releasing heat, and the other part of hydrogen is absorbed into the metal hydrogen storage material through the hydrogen absorption process.
In practical application, the cold energy generated by the B1 metal hydrogen storage material reaction bed 1 and the B2 metal hydrogen storage material reaction bed 2 in the hydrogen releasing and heat absorbing process can be utilized to directly cool and liquefy the hydrogen entering from the liquefying inlet in a direct heat exchange mode; and the heat generated by the B1 metal hydrogen storage material reaction bed 1 and the B2 metal hydrogen storage material reaction bed 2 in the hydrogen absorption and heat release processes can be utilized to directly heat the hydrogen entering from the heat exchange inlet in a direct heat exchange mode.
In practical application, three or more metal hydrogen storage material reaction beds can be arranged, and the metal hydrogen storage material reaction beds can be operated in any combination of switching modes such as 'two absorption and one release' (two reaction beds carry out hydrogen absorption operation and the other reaction bed carries out hydrogen release operation) or 'two absorption and release', so as to adapt to the working condition of inconsistent hydrogen absorption/release reaction rates.
The metallic hydrogen storage materials filled in the B1 metallic hydrogen storage material reaction bed 1 and the B2 metallic hydrogen storage material reaction bed 2 are the same, and the two are alternately operated for absorbing/releasing hydrogen. The specific working process is as follows:
the metal hydrogen storage material B of the metal hydrogen storage material reaction bed 1B 1 absorbs heat at the temperature of 252.5 ℃ below zero and releases liquid hydrogen with the pressure of 0.12MPa, the hydrogen release rate is 0.009kg/s, and simultaneously hydrogen with the pressure of 0.017kg/s after heat exchange at the outlet of a hydrogen expander enters the metal hydrogen storage material reaction bed 1B 1 and is completely condensed into liquid hydrogen with the temperature of 252.5 ℃ below zero; liquid hydrogen with the temperature of 252.5 ℃ below zero and the pressure of 0.12MPa is compressed to 2.6MPa and the pressure of-251.3 ℃ through a liquid hydrogen high-pressure pump 19, and the flow rate is 0.026 kg/s; liquid hydrogen at 2.6MPa and-251.3 ℃ at the outlet of the liquid hydrogen high-pressure pump 19 exchanges heat with hydrogen in the tube pass of the heat exchanger 33, the temperature is raised to-234.8 ℃, hydrogen at-234.8 ℃ and 2.6MPa enters from a second hydrogen absorption inlet 22 'of the B2 metal hydrogen storage material reaction bed 2, wherein 0.009kg/s of hydrogen is absorbed by the B2 metal hydrogen storage material reaction bed 2, the rest 0.017kg/s of hydrogen absorbs the hydrogen absorption reaction heat of the B2 metal hydrogen storage material reaction bed 2 and then is further raised to-195 ℃, hydrogen at-195 ℃, 2.6MPa and 0.017kg/s are sent from a second heat exchange outlet 23' of the B2 metal hydrogen storage material reaction bed 2 to the hydrogen heat exchanger 3 to exchange heat with the hydrogen from a primary expansion outlet of the hydrogen expander 18 and then is raised to-98.1 ℃, and then enters the air heat exchanger 14 to exchange heat with protective nitrogen and atmospheric environment air in the protective cover 28 to-10 ℃ in sequence, the hydrogen after temperature rise enters a hydrogen expander 18 to do work through expansion, the pumping pressure of the hydrogen expander 18 is 0.36MPa, 0.017kg/s and 2.6MPa, the hydrogen at the temperature of minus 10 ℃ is firstly expanded to 0.36MPa and minus 82.1 ℃, then the hydrogen is completely pumped out from a primary expansion outlet, sent to a tube pass of a hydrogen heat exchanger 3 to be subjected to heat exchange and temperature reduction to minus 180 ℃, then sent back to the hydrogen expander from a second expansion inlet to be subjected to secondary expansion, finally expanded to 0.12MPa and minus 199.4 ℃, discharged from a second expansion outlet, and the hydrogen at the temperature of 0.12MPa and minus 199.4 ℃ is cooled to minus 242 ℃ through a heat exchanger 33 and sent to a first liquefaction inlet 32 of a B1 metal hydrogen storage material reaction bed 1 to be cooled and liquefied; when the B1 metal hydrogen storage material reaction bed 1 finishes discharging hydrogen and the B2 metal hydrogen storage material reaction bed 2 finishes absorbing hydrogen, the two are switched between hydrogen absorption and hydrogen discharge. After switching, the work flow of the B2 metallic hydrogen storage material reaction bed 2 is similar to the work flow of the B1 metallic hydrogen storage material reaction bed 1. The work output of the whole system is 13.2 kW.
As shown in fig. 2, the metal hydrogen storage material of this embodiment is a metal hydrogen storage material working combination with positive temperature correlation, and has a hydrogen absorption state point of-195 ℃ and 1.1MPa, and releases heat when absorbing hydrogen, and a hydrogen release state point of-252.5 ℃ and 0.25MPa, and provides low-temperature cold when releasing hydrogen. In order to improve the hydrogen absorption and desorption rate of the metal hydrogen storage material reaction bed, in actual work, the working pressure in the reaction bed is 2.6MPa when hydrogen is absorbed, and the working pressure in the reaction bed is 0.12MPa when hydrogen is desorbed. The dashed line in fig. 2 is the metal hydride state curve, and the solid line in fig. 2 is the metal hydride working curve. The parameters of the hydrogen absorption/desorption state point and the working point of the metal hydrogen storage material can be adjusted at will according to the process requirements.
In one embodiment, the metallic hydrogen storage materials in the B1 metallic hydrogen storage material reaction bed 1 and the B2 metallic hydrogen storage material reaction bed 2 are the same in filling amount and different in filling amount, and the hydrogen absorption/desorption operation is alternately realized through valve switching. The amount of the metal hydrogen storage material filled in the single metal hydrogen storage material reaction bed is allowed to have redundancy, so that the hydrogen absorbing and releasing rate at each time can meet the requirement of rapid high-low pressure switching, and the redundancy equivalent multiple can be adjusted according to the process conditions (1-time redundancy equivalent refers to the minimum amount of the metal hydrogen storage material required when the metal hydrogen storage material is saturated by absorbing hydrogen at a time in the whole complete process cycle).
Specifically, the hydrogen storage materials of the B1 metal hydrogen storage material reaction bed 1 and the B2 metal hydrogen storage material reaction bed 2 include but are not limited to titanium-based metal hydrogen storage materials, and the specific hydrogen storage material can be titanium iron hydride. The total hydrogen absorption and desorption amount of the B1 metal hydrogen storage material reaction bed 1 and the B2 metal hydrogen storage material reaction bed 2 is 9g/s, and the required metal hydrogen storage material is 900 g/s. Accounting according to the hydrogen absorption and desorption time of one time of the metal hydrogen storage material being 50s and the redundancy of the metal hydrogen storage material being 5 times, wherein the hydrogen absorption and desorption switching period is 10s, and the required metal hydrogen storage material is 9kg and the volume is 3.33L; the saturation of the newly added metal hydrogen storage material is 50%, the saturation is 70% after hydrogen absorption, and the saturation is recovered to 50% after hydrogen desorption.
Allowing for a brief heating of at least one statepoint of the metallic hydrogen storage material within each cycle or interval of cycles to restore the kinetic properties of the metallic hydrogen storage material, thereby accelerating the rate of hydrogen absorption and desorption of the metallic hydrogen storage material.
When hydrogen is absorbed and released at the working point β of the B2 metal hydrogen storage material reaction bed 2, part of the hydrogen entering the B2 metal hydrogen storage material reaction bed 2 and lower than the working point β of the B2 metal hydrogen storage material reaction bed 2 is absorbed into the metal hydrogen storage material in the B2 metal hydrogen storage material reaction bed 2, the rest of the hydrogen is raised in temperature and flows out of the B2 metal hydrogen storage material reaction bed 2 to the air heat exchanger 14, the metal hydrogen storage material is strictly limited in the grating in the B2 metal hydrogen storage material reaction bed 2, and any metal hydrogen storage material particles are not allowed to overflow out of the grating, meanwhile, the B1 metal hydrogen storage material reaction bed 1 is in the working point β for hydrogen release process, only the hydrogen is allowed to flow out of the B1 metal hydrogen storage material reaction bed 1, the metal hydrogen material is strictly limited in the grating in the B1 metal hydrogen storage material reaction bed 1, only the liquid hydrogen and a small amount of the gaseous hydrogen is allowed to flow out of the metal hydrogen storage material reaction bed 1, and other indirect heat exchange reaction modes can also be adopted.
The metallic hydrogen storage material stored in the B1 metallic hydrogen storage material reactor bed 1 and the B2 metallic hydrogen storage material reactor bed 2 may be any combination of any particle size, and at the same time, the metallic hydrogen storage material may be solid or hollow. The protective cover 28 may be filled with other gases including, but not limited to, hydrogen, nitrogen, etc., or a mixture thereof.
Claims (7)
1. A metal hydride ultralow temperature circulating work doing system is characterized in that: the system comprises a protective cover (28), and a B1 metal hydrogen storage material reaction bed (1), a B2 metal hydrogen storage material reaction bed (2), a hydrogen heat exchanger (3), a heat exchanger (33), an air heat exchanger (14), a hydrogen expander (18) and a liquid hydrogen high-pressure pump (19) which are arranged in the protective cover (28);
a first hydrogen discharge outlet (21) of the B1 metal hydrogen storage material reaction bed (1) and a second hydrogen discharge outlet (21 ') of the B2 metal hydrogen storage material reaction bed (2) are respectively connected with an inlet of the liquid hydrogen high-pressure pump (19), an outlet of the liquid hydrogen high-pressure pump (19) is connected with a shell-side inlet of the heat exchanger (33), and a shell-side outlet of the heat exchanger (33) is respectively connected with a first hydrogen absorption inlet (22) of the B1 metal hydrogen storage material reaction bed (1) and a second hydrogen absorption inlet (22') of the B2 metal hydrogen storage material reaction bed (2);
a first heat exchange outlet (23) of the B1 metal hydrogen storage material reaction bed (1) and a second heat exchange outlet (23') of the B2 metal hydrogen storage material reaction bed (2) are respectively connected with a shell-side inlet of the hydrogen heat exchanger (3), a shell-side outlet of the hydrogen heat exchanger (3) is connected with a shell-side inlet of the air heat exchanger (14), a shell-side outlet of the air heat exchanger (14) is connected with an inlet of the hydrogen expander (18), a primary expansion outlet of the hydrogen expander (18) is connected with a tube-side inlet of the hydrogen heat exchanger (3), a tube-side outlet of the hydrogen heat exchanger (3) is connected with a secondary expansion inlet of the hydrogen expander (18), a secondary expansion outlet of the hydrogen expander (18) is connected with a hydrogen storage tube-side inlet of the heat exchanger (33), and a tube-side outlet of the heat exchanger (33) is connected with a first liquefaction inlet (32) and a B2 metal material reaction bed (1) of the B1 metal hydrogen storage material reaction bed (1) The second liquid inlet (32') of the material reaction bed (2) is connected;
a nitrogen heat exchange coil (4) and an air heat exchange coil (5) are arranged in the air heat exchanger (14), a tube pass inlet and a tube pass outlet of the nitrogen heat exchange coil (4) are both arranged in the protective cover (28), and a tube pass inlet and a tube pass outlet of the air heat exchange coil (5) are both arranged outside the protective cover (28);
the B1 metal hydrogen storage material reaction bed (1) and the B2 metal hydrogen storage material reaction bed (2) are both provided with an internal circulation bypass, the internal circulation bypass is provided with a hydrogen medium internal circulation pump (7), and when the metal hydrogen storage material reaction bed performs hydrogen absorption and hydrogen desorption operations, the circulation reciprocation of the hydrogen medium in the B1 metal hydrogen storage material reaction bed (1) and the B2 metal hydrogen storage material reaction bed (2) is realized, so that the operation working condition is stabilized.
2. The metal hydride ultralow temperature cycle work system as set forth in claim 1, wherein: the system further comprises a generator (17); the hydrogen expander (18) is coaxially connected with a generator (17), and the generator (17) is electrically connected with an external power grid and/or a storage battery; the hydrogen expander (18) includes, but is not limited to, rotary impeller and piston work machines.
3. The metal hydride ultralow temperature cycle work system as set forth in claim 1, wherein the heat exchange in the B1 metal hydrogen storage material reaction bed (1) and the B2 metal hydrogen storage material reaction bed (2) adopts a mode that hydrogen directly enters the metal hydrogen storage material reaction bed for heat exchange, when hydrogen is absorbed and releases heat at the operating point β of the B2 metal hydrogen storage material reaction bed (2), a part of hydrogen entering the B2 metal hydrogen storage material reaction bed (2) is absorbed into the metal hydride in the B2 metal hydrogen storage material reaction bed (2), the rest hydrogen temperature is increased and carries heat out of the B2 metal hydrogen storage material reaction bed (2) to enter the air heat exchanger (14), the metal hydride is strictly limited in the grid in the B2 metal hydrogen storage material reaction bed (2), no metal hydride particles are allowed to overflow out of the grid, only hydrogen or liquid hydrogen is allowed to enter and exit, the B1 metal hydrogen storage material reaction bed (1) is subjected to hydrogen desorption process, only hydrogen is allowed to enter and exit the metal hydride material reaction bed (2), only the metal hydride is allowed to change into the metal hydride reaction bed (891) and only to react with a small amount of metal hydride material after hydrogen absorption and heat absorption at the operating point 6338, the metal hydride reaction bed (2) is changed into the metal hydride metal hydrogen absorption reaction bed (3636) and the metal hydrogen absorption point 3636;
the B1 metal hydrogen storage material reaction bed (1) and the B2 metal hydrogen storage material reaction bed (2) are used for cooling and liquefying hydrogen entering from a hydrogen inlet and cooling and liquefying hydrogen released by the metal hydrogen storage material when hydrogen is released and absorbed at low temperature and low pressure; the B1 metal hydrogen storage material reaction bed (1) and the B2 metal hydrogen storage material reaction bed (2) are used for further heating treatment of a part of hydrogen entering from the heat exchange inlet when absorbing hydrogen at high temperature and high pressure and releasing heat, and the other part of hydrogen is absorbed and enters the metal hydrogen storage material.
4. The metal hydride ultralow temperature cycle work system as set forth in claim 1, wherein: the metal hydrides filled in the B1 metal hydrogen storage material reaction bed (1) and the B2 metal hydrogen storage material reaction bed (2) are the same, the filling amount is allowed to be the same or different, the hydrogen absorption/desorption operation of the metal hydrides and the metal hydrides is alternately realized by switching valves, and the switching frequency can be adjusted according to the process conditions; the amount of metal hydride filled in a single metal hydrogen storage material reaction bed is allowed to have redundancy, so that the hydrogen absorbing and releasing rate of each time can meet the requirement of rapid high-low pressure switching, and the redundancy equivalent multiple can be adjusted according to the process conditions; the 1-fold redundant equivalent is the minimum amount of the metal hydrogen storage material required when the metal hydrogen storage material is saturated by absorbing hydrogen once in the whole complete process cycle; the metal hydride stored in the B1 metal hydrogen storage material reaction bed (1) and the B2 metal hydrogen storage material reaction bed (2) can be any combination of any particle size, and at the same time, the metal hydride can be solid or hollow.
5. The metal hydride ultralow temperature cycle work system as set forth in claim 1, wherein: the protective cover (28) is provided with a combustible gas alarm (29) and a protective gas inlet (27), the protective gas inlet (27) is provided with a valve, and gas filled in the protective cover (28) comprises but is not limited to hydrogen, nitrogen and helium.
6. The metal hydride ultralow temperature cycle work system as set forth in claim 1, wherein: besides using gaseous hydrogen as a circulating heat exchange medium of a work-doing system, other gases can be used as the circulating heat exchange medium; in addition, other substances including but not limited to stable solids, liquids or liquid organic hydrides can be used instead of hydrogen as the circulating heat exchange medium of the work-doing system; the heat exchange mode can be direct heat exchange or partition wall heat exchange, and the heat exchange medium for partition wall heat exchange can be gas, liquid, solid or a mixture of the above or a mixture of every two; the metal hydride work including but not limited to positive temperature correlation is defined as absorbing high-pressure hydrogen at high temperature to release high-temperature heat and releasing low-pressure hydrogen at low temperature to release low-temperature cold; absorbing hydrogen to release high-temperature heat at high temperature, and utilizing the metal hydrogen storage material reaction bed to directly exchange heat to heat the working hydrogen; the system at least has one negative pressure unit, or the negative pressure of metal hydride, or the negative pressure of hydrogen liquefaction, or the combination of the above negative pressures; the heat exchange of the working hydrogen at low temperature is to absorb heat when the metal hydride releases low-pressure hydrogen at low temperature, and the low-temperature cold energy generated by the metal hydride is used for cooling the working hydrogen for liquefaction; the system equipment and the pipeline are provided with external heat preservation, internal heat preservation and internal and external heat preservation;
the system comprises a circulating work system consisting of at least one metal hydride, at least one negative pressure unit including the metal hydride, a circulating work system consisting of at least one negative pressure unit including the metal hydride, at least one metal hydride which is switched between high pressure and low pressure and comprises but is not limited to the circulating work system with positive temperature correlation, a high temperature point β 2 of the metal hydride comprises but is not limited to any temperature lower than the ambient temperature, a low temperature point β 1 of the metal hydride comprises but is not limited to lower than the liquefaction temperature of hydrogen or comprises but is not limited to the vicinity of the liquefaction temperature of hydrogen, the metal hydride comprises but is not limited to titanium metal hydride, at least one state point of the metal hydride is allowed to be heated temporarily in each cycle or at intervals of the cycles so as to recover the dynamic performance of the metal hydride, thereby the hydrogen absorption and release speed of the metal hydride is increased, the hydrogen absorption/release state point and the working point parameters of the metal hydrogen storage material can be adjusted arbitrarily according to the process requirements, the system also allows a protective cover (28) to remove the heat energy input into the system, the air heat exchanger (14), the metal hydride reaction bed can be provided with three or more than two metal hydride reaction beds, thereby the metal hydride can be operated in a switching mode of any combination of 'two absorption and release energy' two absorption and two hydrogen release 'reaction bed' the hydrogen absorption and the hydrogen reaction bed 'can be used as a natural energy' communication device, thereby realizing the hydrogen absorption and two reaction device which can be used for realizing the hydrogen absorption and two reaction system and can be used for realizing the simultaneous operation of the same reaction system, thereby realizing the hydrogen absorption and release system can be used as a similar.
7. The metal hydride ultralow temperature cycle work system as set forth in claim 1, wherein: the system also comprises a metal hydrogen storage material replacing device (6), wherein the metal hydrogen storage material replacing device (6) is used for taking out and filling the metal hydrogen storage materials in the B1 metal hydrogen storage material reaction bed (1) and the B2 metal hydrogen storage material reaction bed (2); the metal hydrogen storage material replacing device (6) comprises a separation tank (114), a recovery tank (115), a residual hydrogen absorption unit (116), a vacuum tank (117), a protective gas compressor (119), a high-pressure protective gas tank (120), a raw material tank (123), a feeder (124), an extraction metering instrument (126), an addition metering instrument (127) and a filling gun (111); the filling gun (111) is provided with a sealing ring and a locking flange, the adding and extracting ports of the B1 metal hydrogen storage material reaction bed (1) and the B2 metal hydrogen storage material reaction bed (2) are provided with stop valves with coded locks, and the filling gun (111) is hermetically connected with the adding and extracting port of the B1 metal hydrogen storage material reaction bed (1) or the B2 metal hydrogen storage material reaction bed (2) through the locking flange; the filling gun (111) is provided with a feeding-discharging port which is connected to a separation tank (114) through an adding-pumping shared pipeline (125) and a pumping-out pipeline (122), a solid outlet of the separation tank (114) is connected to a recovery tank (115) through a pumping-out metering instrument (126), a gas outlet of the separation tank (114) is connected to a vacuum tank (117) through a residual hydrogen absorption unit (116), the vacuum tank (117) is connected to a high-pressure protective gas tank (120) through a one-way valve (39) and a protective gas compressor (119), an outlet of the high-pressure protective gas tank (120) is divided into two paths, one path is connected to a feeder (124), one path is connected to a protective gas inlet of the filling gun (111) through a protective gas pipeline (121), and a raw material tank (123) is connected to the feeding-discharging port of the filling gun (111) through the feeder (124), the adding metering instrument (127), the adding pipeline (128) and the adding-pumping shared pipeline (125); the purpose of using the metal hydrogen storage material replacing device (6) to extract the metal hydrogen storage material comprises but is not limited to replacing the metal hydrogen storage material to recover the hydrogen absorption and desorption performance thereof, or heating the metal hydrogen storage material to increase the hydrogen absorption and desorption kinetic performance.
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