CN114719185B - Hydrogen slurry reaction device and hydrogen storage and release method - Google Patents
Hydrogen slurry reaction device and hydrogen storage and release method Download PDFInfo
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- CN114719185B CN114719185B CN202210334601.0A CN202210334601A CN114719185B CN 114719185 B CN114719185 B CN 114719185B CN 202210334601 A CN202210334601 A CN 202210334601A CN 114719185 B CN114719185 B CN 114719185B
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
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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
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C13/00—Details of vessels or of the filling or discharging of vessels
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C13/00—Details of vessels or of the filling or discharging of vessels
- F17C13/04—Arrangement or mounting of valves
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C5/00—Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C7/00—Methods or apparatus for discharging liquefied, solidified, or compressed gases from pressure vessels, not covered by another subclass
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
- F17C2205/03—Fluid connections, filters, valves, closure means or other attachments
- F17C2205/0302—Fittings, valves, filters, or components in connection with the gas storage device
- F17C2205/0323—Valves
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/01—Pure fluids
- F17C2221/012—Hydrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
- F17C2250/03—Control means
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The embodiment of the invention provides a hydrogen slurry reaction device and a hydrogen storage and release method, wherein the reaction device comprises: the hydrogen storage material is circularly subjected to hydrogen storage reaction and hydrogen release reaction in the first body and the second body. According to the invention, hydrogen is absorbed and released through coupling of the liquid organic material and the solid alloy powder, meanwhile, the solid alloy powder is used as a catalyst for hydrogen storage reaction and hydrogen release reaction of the liquid organic material, the liquid organic material is used as a dispersion carrier of the solid alloy powder, the pulverization influence of the solid alloy powder is considered, the mass ratio of the liquid organic material to the solid alloy powder and the flow of the liquid organic material can be adjusted according to the change of the particle size distribution of the solid alloy powder, the operation parameters are adjusted accordingly, the contact area of hydrogen and the hydrogen storage material is increased, the optimization of operation is realized, and the optimal airspeed and reaction efficiency are achieved.
Description
Technical Field
The invention relates to the technical field of hydrogen energy storage and release, in particular to a hydrogen slurry reaction device and a hydrogen storage and release method.
Background
In hydrogen energy application, the on-demand storage and release of hydrogen are important problems affecting the safety and cost of hydrogen utilization, how to store hydrogen becomes a popular research direction, the most widely used gaseous hydrogen at present has the problems of poor safety and low hydrogen storage density, and in large-scale hydrogen energy storage application, the explosion hazard and the oversized storage tank can cause great promotion of occupation and management cost; and the hydrogen is not thoroughly released from the gas-hydrogen storage tank, so that a certain residual hydrogen amount is lost, and the release speed is reduced due to the fact that the residual pressure of the gas cylinder is reduced in the later stage of the hydrogen release process.
In the prior art, both organic liquid and solid alloy are used as hydrogen storage materials for research, wherein although the solid alloy or the organic liquid and the like are used as the hydrogen storage materials to realize large-scale and long-period storage of hydrogen and can be stored at normal temperature and normal pressure with high safety, the organic liquid hydrogen storage not only has the problems of poor hydrogen absorption and desorption dynamics performance and higher temperature requirement, but also has smaller contact area with the hydrogen and lower hydrogen storage and desorption efficiency. When the solid alloy is used for storing hydrogen, the solid alloy has a gap, and has a larger hydrogen contact area compared with the organic liquid hydrogen storage, but the contact area with the hydrogen and the hydrogen storage efficiency are gradually reduced along with the pulverization of the solid alloy in 100 reaction cycles, namely from the average particle size of 50-100 micrometers to about 1 micrometer. Therefore, how to provide a hydrogen slurry reaction device to realize the storage and release of hydrogen according to the needs and achieve the optimal space velocity and reaction efficiency is a technical problem which needs to be solved by the person skilled in the art.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent.
Therefore, the invention aims to provide a hydrogen slurry reaction device, wherein a hydrogen storage material circularly carries out a hydrogen storage reaction and a hydrogen release reaction in a first body and a second body.
In order to achieve the above object, an embodiment of the present invention provides a hydrogen slurry reaction apparatus, including:
a first body having a volume of hydrogen storage material contained therein;
the input end of the second body is connected with the output end of the hydrogen storage material of the first body, and the output end of the second body is connected with the input end of the hydrogen storage material of the first body; the hydrogen storage material circularly flows in the first body and the second body;
a heating unit that heats the first body and the second body, respectively; and
a microfiltration assembly; the input end of the device is connected with the output end of the second body, and the output end of the device is connected with the input end of the hydrogen storage material of the first body, and the device is used for screening the circulating hydrogen storage material.
In some embodiments, a hydrogen inlet and a first hydrogen outlet are formed in the height direction of the first body, wherein the hydrogen inlet and the first hydrogen outlet are oppositely arranged; and a second hydrogen outlet is formed in the second body.
In some embodiments, the reaction device further comprises a plurality of sampling windows dispersed on the connecting lines of the first body and the second body.
In some embodiments, the hydrogen storage material comprises a liquid organic material and a solid alloy powder in a mass ratio of 5-10:1; wherein the liquid organic material is an aromatic liquid organic material; the solid alloy powder is a rare earth series AB 5 At least one of a zirconium alloy, a titanium alloy, a vanadium alloy and a magnesium alloy.
In some embodiments, the first body further includes a first fill port and a second fill port thereon; the first filling port is used for inputting the liquid organic material into the first body; the second charging port is used for inputting the solid alloy powder into the first body.
In some embodiments, the first body and the second body are provided with a drain outlet, and the drain outlet is used for discharging the hydrogen storage material after use.
The embodiment of the invention also provides a hydrogen storage control method, which comprises the following steps:
assembling the reaction apparatus described in any of the above embodiments;
introducing a flow of liquid organic material and solid alloy powder into the first body until it circulates steadily in the first body and the second body;
heating the first body and the second body, and then introducing hydrogen with certain pressure into the first body;
periodically monitoring the particle size of the solid alloy powder, and adjusting the mass ratio of the liquid organic material to the solid alloy powder and the flow rate of the liquid organic material according to the particle size change of the solid alloy powder.
In some embodiments, the initial volumetric flow rate Q of the liquid organic material 0 ＝V*TOF；
Wherein Q is 0 The unit is L/min; v is the sum of the volumes of the first body and the second body, and the unit is L; TOF is the space velocity of the hydrogen storage reaction and the hydrogen release reaction of the liquid organic material and the solid alloy powder, and the unit is min -1 ；
TOF＝k*m l /m g ；
Wherein k is the speed constant of the hydrogen storage reaction and the hydrogen release reaction of the liquid organic material and the solid alloy powder, and the unit is min -1 ；m l The unit is kg of the mass of the liquid organic material; m is m g The unit is kg for the mass of the solid alloy powder.
In some embodiments, a method of adjusting a mass ratio of a liquid organic material to a solid alloy powder according to a change in particle size of the solid alloy powder comprises:
when the particle diameter d of the solid alloy powder m With an initial particle diameter d 0 The ratio of (2) is 1:20-50, the particle diameter d is used 0 The solid alloy powder replacement particle diameter of d m The solid alloy powder of (2) has a particle diameter d m The mass percentage of the solid alloy powder to be replaced is 20-80% based on the mass of the solid alloy powder;
obtaining a relation formula of solid alloy powder particle size-airspeed-liquid organic material flow in the newly formed hydrogen storage material;
TOF adjustment of ＝f(d)；
Wherein TOF is Adjustment of Space velocity in min for hydrogen storage reaction and hydrogen release reaction of the newly formed hydrogen storage material -1 The method comprises the steps of carrying out a first treatment on the surface of the Q=f (d), Q being the volumetric flow rate of the liquid organic material in L/min;
Q adjustment of ＝V*TOF Adjustment of ＝V*f(d)
Wherein Q is Adjustment of The unit is L/min for the volume flow of the liquid organic material after adjustment; TOF (time of flight) Adjustment of Space velocity in min for hydrogen storage reaction and hydrogen release reaction of the newly formed hydrogen storage material -1 The method comprises the steps of carrying out a first treatment on the surface of the V is the first body and the second bodyThe sum of the volumes of the bodies is given in L.
In some embodiments, Q is defined Adjustment of >2Q 0 In the time-course of which the first and second contact surfaces,
wherein Q is Adjustment of For the volume flow of the regulated liquid organic material; q (Q) 0 An initial volumetric flow rate for the liquid organic material; m is m l An initial mass of the liquid organic material; m is m g An initial mass of the solid alloy powder; m is m l-tone The mass of the liquid organic material is regulated according to the particle size of the solid alloy powder; m is m g-shape regulating device The mass of the solid alloy powder is regulated according to the particle size of the solid alloy powder.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic diagram of a hydrogen slurry reaction apparatus according to an embodiment of the present invention.
FIG. 2 is a schematic structural view of a hydrogen slurry reaction apparatus according to another embodiment of the present invention.
FIG. 3 is a schematic view showing a hydrogen slurry reaction apparatus according to another embodiment of the present invention.
FIG. 4 is a schematic structural view of a hydrogen slurry reaction apparatus according to another embodiment of the present invention.
FIG. 5 is a flow chart showing a method for controlling hydrogen storage in a hydrogen slurry reaction apparatus according to an embodiment of the present invention.
Reference numerals:
a reaction apparatus 100;
a first body 1; a hydrogen inlet 11; a first hydrogen outlet 12; a first charging port 13; a second charging port 14; a drain outlet 15;
a second body 2; a second hydrogen outlet 21; a valve 22;
a heating assembly 3;
a microfiltration assembly 4;
Detailed Description
The present invention will be described in further detail with reference to examples in order to make the objects, technical solutions, and advantages of the present invention more apparent. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other technical solutions obtained by a person skilled in the art based on the embodiments of the present invention fall within the scope of protection of the present invention.
As shown in fig. 1 to 5, the present invention is directed to a hydrogen slurry reaction apparatus 100, in which a hydrogen storage material circulates in a first body 1 and a second body 2 to perform a hydrogen storage reaction and a hydrogen discharge reaction, and the coupling of a liquid organic material and a solid alloy powder is used to absorb and discharge hydrogen, and considering the pulverization effect of the solid alloy powder, the mass ratio of the liquid organic material to the solid alloy powder and the flow rate of the liquid organic material can be adjusted according to the change of the particle size distribution of the solid alloy powder, so that the contact area between hydrogen and the hydrogen storage material can be increased, the operation can be optimized, and the optimal airspeed and reaction efficiency can be achieved.
To achieve the above object, as shown in fig. 1, an embodiment of the present invention provides a hydrogen slurry reaction apparatus 100, including: a first body 1, a second body 2, a heating assembly 3 and a micro-filtration assembly 4; wherein a certain volume of hydrogen storage material is filled in the first body 1, and the output end of the hydrogen storage material of the first body 1 is connected with the input end of the hydrogen storage material of the second body 2; the output end of the hydrogen storage material of the second body 2 is connected with the input end of the hydrogen storage material of the first body 1; the hydrogen storage material may circulate within the first body 1 and the second body 2. The hydrogen slurry reaction device 100 in this embodiment further includes a pump device, and the hydrogen storage material can be conveyed to smoothly circulate in the first body 1 and the second body 2. In this embodiment, the hydrogen storage material circulates in the first body 1 and the second body 2, so that the contact surface between the hydrogen and the hydrogen storage material is further increased, and the proceeding degree of the hydrogen storage reaction and the hydrogen release reaction is improved.
The heating component 3 in this embodiment can heat the first body 1 and the second body 2 respectively, and as will be understood by those skilled in the art, the hydrogen storage reaction and the hydrogen release reaction performed by using the hydrogen storage material need to be performed at a certain temperature and pressure, and the heating component 3 in this embodiment can be a heating sleeve, a heating pipe or other equipment with a heating function and controllable temperature, and can heat the first body 1 and the second body 2, and provide a suitable temperature and pressure for the hydrogen storage material circulated in the first body 1 and the second body 2 to perform the hydrogen storage reaction or the hydrogen release reaction.
The microfiltration assembly 4 is used for screening the circulating hydrogen storage material, and the input end of the hydrogen storage material is connected with the output end of the hydrogen storage material of the second body 2, and the output end of the hydrogen storage material is connected with the input end of the hydrogen storage material of the first body 1. It can be understood that the micro-filtration assembly 4 is internally provided with a micro-filtration net, so that the hydrogen storage material can be screened out and unqualified hydrogen storage material can be screened out, and unqualified hydrogen storage material is prevented from continuously circulating in the first body 1 and the second body 2, so that the hydrogen storage reaction and the hydrogen release reaction efficiency are affected.
It should be noted that in this embodiment, the valves 22 are disposed on the pipes connecting the first body 1, the second body 2 and the micro-filtration assembly 4, and as shown in fig. 2, the valves 22 are disposed to facilitate flow control and sampling.
In some embodiments, a hydrogen inlet 11 and a first hydrogen outlet 12 are formed in the height direction of the first body 1; the second body 2 is provided with a second hydrogen outlet 21.
It is easy to understand that this embodiment will be described by taking the case where the height direction of the first body 1 coincides with the up-down direction, which is shown in fig. 1.
Specifically, as shown in fig. 1, a first hydrogen outlet 12 for releasing hydrogen is formed above the first body 1, and a hydrogen inlet 11 for entering hydrogen is formed below the first body 1. It can be understood that a certain volume of hydrogen storage material can be contained in the first body 1, hydrogen is introduced from the hydrogen inlet 11 of the first body 1, the pressure of the introduced hydrogen is controlled through the compressor and the valve 22, the heating component 3 is utilized to enable the first body 1 and the second body 2 to reach a certain temperature, the hydrogen storage reaction can occur, the hydrogen storage material circulates in the first body 1 and the second body 2, the contact surface of the hydrogen and the hydrogen storage material is further increased, and the hydrogen storage reaction efficiency is improved; similarly, in this embodiment, the second body 2 is provided with the second hydrogen outlet 21, and if a hydrogen releasing reaction occurs, only the corresponding temperature and pressure need to be changed, and the hydrogen released by the hydrogen storage material can be collected through the first hydrogen outlet 12 and the second hydrogen outlet 21.
In some embodiments, the hydrogen storage material comprises a liquid organic material and a solid alloy powder in a mass ratio of 5-10:1; wherein the liquid organic material is an aromatic liquid organic material; the solid alloy powder is rare earth AB 5 At least one of a zirconium alloy, a titanium alloy, a vanadium alloy and a magnesium alloy.
Illustratively, the liquid organic material and the solid alloy powder in the hydrogen storage material are in a mass ratio of 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or any range therebetween. When the mass ratio of the liquid organic material of the hydrogen storage material to the solid alloy powder is too low (for example, the mass ratio is lower than 5), the dispersion of solid particles is insufficient, the liquid fixedly connected thixotropic is poor, the reaction efficiency is reduced, and the solid utilization rate is reduced; when the mass ratio of the liquid organic material to the solid alloy powder is too high (for example, the mass ratio is higher than 10), the solid alloy powder is too small in unit volume, the hydrogen storage and release amount which can be achieved by the device is low, and the processing capacity of the device is reduced. Preferably, the initial particle diameter d of the solid alloy powder in the hydrogen storage material 0 50-100 μm, e.g. primary particle size d of solid alloy powder 0 50, 60, 70, 80, 90, 100 microns or any range therebetween.
Specifically, the aromatic liquid organic material comprises at least one of benzene series, carbazole series and indole series; wherein, for example, the benzene system can be at least one selected from cyclohexane, methylcyclohexane, benzene, toluene and the like; exemplary carbazole groups may be selected from, for example, ethylcarbazole,At least one of tetrahydrocarbazole, octahydrocarbazole, dodecahydrocarbazole, etc.; exemplary indole systems may be selected from N-ethylindole, N-methylindole, and the like. The solid alloy in this embodiment is a rare earth AB 5 Alloys such as LaNi 5 Zirconium alloys such as ZrMn 2 Titanium-based alloys such as TiFe, vanadium-based alloys such as VFe, magnesium-based alloys such as Mg 2 Ni, and the like.
The hydrogen storage material in this embodiment is exemplified by N-ethylindole as the liquid organic material, laNi 5 When the alloy is solid alloy powder, the temperature of hydrogen storage reaction is 160-190 ℃ and the pressure is 2-10MPa; the temperature of the hydrogen release reaction is 170-220 ℃ and the pressure is 0.1-1MPa; for example, ethyl carbazole is used as liquid organic material, mg 2 When Ni is solid alloy powder, the temperature of hydrogen storage reaction is 200-250 ℃ and the pressure is 2-10MPa; the temperature of the hydrogen release reaction is 220-300 ℃ and the pressure is 0.1-1MPa; for example, toluene is used as the liquid organic material, and LaNi 5 When the alloy is solid alloy powder, the temperature of hydrogen storage reaction is 200-250 ℃ and the pressure is 2-10MPa; the temperature of the hydrogen release reaction is 300-350 ℃ and the pressure is 0.1-1MPa.
The embodiment of the invention realizes the coupling absorption and desorption of hydrogen of the liquid organic material and the solid alloy powder, and simultaneously utilizes the solid alloy powder as a catalyst for the hydrogen storage reaction and the hydrogen desorption reaction of the liquid organic material, and the liquid organic material is used as a dispersion carrier of the solid alloy powder. The embodiment realizes the fluidization operation of the hydrogen storage material formed by the liquid organic material and the solid alloy powder, increases the contact area of gas, liquid and solid, and improves the reaction efficiency; the hydrogen storage material circulates through the first body 1 and the second body 2, so that the separation energy consumption of the fine powder substance of the solid alloy powder and the continuous phase, namely the liquid organic material, is avoided, and meanwhile, the reaction part is further increased, and the reaction progress is improved.
In some embodiments, the first body 1 further comprises a first filling port 13 and a second filling port 14; the first filling port 13 is used for inputting liquid organic materials into the first body 1; the second charging port 14 is used for inputting solid alloy powder into the first body 1.
Specifically, as shown in fig. 1 and 2, in this embodiment, the liquid organic material is introduced into the lower portion of the first body 1 through the first filling port 13 and the solid alloy powder through the second filling port 14, the solid-liquid mixture is uniformly dispersed in the first body 1 under the flow lifting action of the liquid organic material, and enters the second body 2 through the pipe, and circulates back into the first body 1 from the second body 2, so that the hydrogen storage material composed of the liquid organic material and the solid alloy powder forms stable solid-liquid distribution and circulation between the first body 1 and the second body 2. Advantageously, a valve 22 is provided at the first filling port 13, the flow rate of the liquid organic material can be regulated by the valve 22, a cock is provided at the second filling port 14, and the discharge amount of the solid alloy powder can be regulated by the cock.
In some embodiments, as shown in fig. 3, the first body 1 and the second body 2 are both provided with a drain 15, and the drain 15 is used for discharging the hydrogen storage material after use. It is understood that in general, in 100 reaction cycles, the solid alloy powder having an average particle diameter of 50 to 100 μm can be pulverized to about 1 μm, which is manifested in a decrease in hydrogen storage and release rate, a decrease in particle diameter, a deterioration in separation effect, and the like. The drain 15 may be used to completely drain solid alloy powder and liquid organic material that do not meet performance requirements after a period of use. Specifically: the hydrogen inlet 11, the first filling inlet 13 and the second filling inlet 14 can be closed, the gas is blown from the first hydrogen outlet 12, and the hydrogen storage material in the first body 1 is discharged from the sewage outlet 159.
In some embodiments, the reaction apparatus 100 further comprises a plurality of sampling windows 5, wherein the sampling windows 5 are distributed on the connecting lines of the first body 1 and the second body 2.
Specifically, as shown in fig. 4, a certain particle size limit value may be set for the solid alloy powder, when the solid alloy powder passes through multiple reaction cycles, the pulverization degree of the solid alloy powder is periodically and regularly detected, if the particle size of the solid alloy powder is pulverized to the limit value, it indicates that the hydrogen storage and release speed is reduced, the particle size is reduced, and the separation effect is poor, and the microfiltration assembly 4 may be used to screen out the solid alloy powder in the circulating hydrogen storage material and to re-fill with new solid alloy powder with excellent functions. The method comprises the following steps: the pulverization degree of the solid alloy powder is periodically detected through the sampling window 5, when the real-time analysis result of the particle size of the solid alloy powder shows that the particle size is reduced to the particle size limit value, the pipe valve 22 between the second body 2 and the micro-filtration assembly 4 is opened, a part of the solid alloy powder is removed through the micro-filtration assembly 4, and simultaneously, an equivalent amount of new solid alloy powder excellent in function is replenished from the lower part of the second charging port 14 of the first body 1, and the replacement rate of the solid alloy powder is preferably 20-80%. In the embodiment, the influence of solid alloy powder pulverization on the catalytic efficiency and the hydrogen absorption and desorption reaction rate is considered, the particle size is analyzed in real time by arranging the sampling port, and the operation parameters are adjusted accordingly, so that the operation optimization is realized.
As shown in fig. 5, according to an embodiment of the present invention, there is also provided a hydrogen storage control method, including the steps of:
s1, assembling the reaction device 100 in any embodiment;
s2, introducing a certain flow of liquid organic material and solid alloy powder into the first body 1 until the liquid organic material and the solid alloy powder circulate stably in the first body 1 and the second body 2;
s3, heating the first body 1 and the second body 2, and then introducing hydrogen with certain pressure into the first body 1;
and S4, periodically monitoring the particle size of the solid alloy powder, and adjusting the mass ratio of the liquid organic material to the solid alloy powder and the flow rate of the liquid organic material according to the particle size change of the solid alloy powder.
Specifically, in S1, the hydrogen slurry reaction apparatus 100 in any of the above embodiments is connected by a pipeline, and a suitable hydrogen storage material is selected, where the initial mass ratio of the liquid organic material to the solid alloy powder is preferably 5-10:1, initial particle diameter d of solid alloy powder 0 Preferably 50-100 μm (see the above and not described again), the total volume V is the sum of the volumes of the first body 1 and the second body 2 in the hydrogen slurry reaction device 100 in this embodiment.
The method for determining the initial flow rate of the liquid organic material with a certain flow rate comprises the following steps:
at the selected hydrogen storage temperature and pressure (or hydrogen release temperature and pressure), detecting the isothermal line of hydrogen storage (or hydrogen release), namely the hydrogen storage amount-time curve (or hydrogen release amount-time curve), of the hydrogen storage material system, wherein the detection method is a conventional method and is not repeated.
Obtaining the speed constant k (min) of the hydrogen storage reaction or the hydrogen release reaction by performing first-order dynamics fitting on the isothermal line of the hydrogen storage (or the hydrogen release) -1 )：
dc/ct＝k(c e -c)
c is the concentration of the hydrogen storage (or desorption) reaction product at time t, and the unit is kg/L, c e The concentration of the hydrogen storage (or hydrogen release) reaction product when the reaction reaches equilibrium is expressed in kg/L;
airspeed of the hydrogen storage reaction and the hydrogen release reaction of the liquid organic material and the solid alloy powder, tof=k×m l /m g ；
Wherein k is the speed constant unit of min for hydrogen storage reaction and hydrogen release reaction of the liquid organic material and the solid alloy powder -1 ；m l The mass of the liquid organic material is Kg; m is m g The mass of the solid alloy powder is kg;
according to the rate constant k (min -1 ) And space velocity TOF (min) of hydrogen storage reaction and hydrogen release reaction of liquid organic material and solid alloy powder -1 ) The initial volume flow Q of the liquid organic material can be obtained 0 ；
Q 0 ＝V*TOF；
Wherein Q is 0 The unit is L/min; v is the sum of the volumes of the first body 1 and the second body 2, and the unit is L; TOF is the space velocity of the hydrogen storage reaction and the hydrogen release reaction of the liquid organic material and the solid alloy powder, and the unit is min -1 。
In some embodiments, the method of adjusting the mass ratio of the liquid organic material to the solid alloy powder according to the particle size variation of the solid alloy powder in S4 comprises:
firstly, the pulverization degree of the solid alloy powder can be analyzed in a real-time analysis mode, namely, the particle size value of the solid alloy powder is measured, specifically: sampling from the sampling window 5 may be performed by on-line or off-line analysis, for example, by focused beam reflectometry, particle recording microscopy, etc.; the off-line mode can be analyzed by means of a laser particle size analyzer, a zeta potentiometer and the like, namely the analysis frequency of the particle size of the solid alloy powder is preferably 10-30 min/time when the off-line mode is performed.
Wherein the volumetric flow rate of the liquid organic material q=f (d);
mass flow rate m=g (d) of the solid alloy powder;
next, when the particle diameter d of the solid alloy powder m With an initial particle diameter d 0 The ratio of (2) is 1:20 to 50, for example, the initial particle diameter d of the solid alloy powder in the present embodiment 0 Preferably 50-100 μm, and the particle size of the solid alloy powder detected by real-time analysis at this stage is d m When the particle diameter is 1-5 micrometers, the particle diameter d can be utilized 0 The solid alloy powder of (2) has a substitution particle diameter d m Wherein the substitution amount is d in particle size m Based on the mass of the solid alloy powder, the alternative particle size is d 0 The solid alloy powder of (2) has a particle diameter d m 20-80% of the mass of the solid alloy powder.
When the new particle diameter d is added 0 After the solid alloy powder of (2) obtaining the relation between the particle size of the solid alloy powder in the newly formed hydrogen storage material and the space velocity of the solid alloy powder and the flow of the liquid organic material;
that is, after a new hydrogen storage material is formed in the present hydrogen slurry reaction apparatus 100, the hydrogen storage material is added to the value d 0 And d m Selecting 6-8 intermediate particle size values at equal intervals, and determining the space velocity TOF according to the method Adjustment of For solid alloy powder and corresponding TOF Adjustment of Fitting the numerical values to obtain a relational expression
TOF Adjustment of ＝f(d)；
Wherein TOF is Adjustment of Space velocity in min for hydrogen storage and desorption reactions for newly formed hydrogen storage material -1 The method comprises the steps of carrying out a first treatment on the surface of the Q=f (d), Q being the flow rate of the liquid organic material in L/min;
Q adjustment of ＝V*TOF Adjustment of ＝V*f(d)
Wherein Q is Adjustment of For conditioned liquid organic materialVolume flow, in L/min; TOF (time of flight) Adjustment of Space velocity in min for hydrogen storage and desorption reactions for newly formed hydrogen storage material -1 The method comprises the steps of carrying out a first treatment on the surface of the V is the sum of the volumes of the first body 1 and the second body 2, in L.
In some embodiments, to avoid excessive flow of liquid organic material, Q is defined Adjustment of >2Q 0 In the time-course of which the first and second contact surfaces,
wherein Q is Adjustment of For the volume flow of the regulated liquid organic material; q (Q) 0 An initial volumetric flow rate of the liquid organic material; m is m l Is the initial mass of the liquid organic material; m is m g Is the initial mass of the solid alloy powder; m is m l-tone The quality of the liquid organic material is regulated according to the particle size of the solid alloy powder; m is m g-shape regulating device The quality of the solid alloy powder is regulated according to the particle size of the solid alloy powder.
The hydrogen storage control method of the hydrogen slurry reaction device 100 of this embodiment considers the influence of pulverization of solid alloy powder on the catalytic efficiency and the hydrogen absorption reaction and hydrogen discharge reaction rate, adjusts the mass ratio of the liquid organic material to the solid alloy powder and the flow rate of the liquid organic material according to the change of the particle size distribution of the solid alloy powder, adjusts the operation parameters accordingly, increases the contact area of hydrogen and the hydrogen storage material, realizes the optimization of the operation, and achieves the optimal airspeed and reaction efficiency.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A hydrogen slurry reaction apparatus, comprising:
a first body having a volume of hydrogen storage material contained therein; the hydrogen storage material comprises a liquid organic material and solid alloy powder in a mass ratio of 5-10:1, and the mass ratio of the liquid organic material to the solid alloy powder is adjusted according to the particle size change of the solid alloy powder;
the input end of the second body is connected with the output end of the hydrogen storage material of the first body, and the output end of the second body is connected with the input end of the hydrogen storage material of the first body; the hydrogen storage material circularly flows in the first body and the second body;
a heating unit that heats the first body and the second body, respectively; and
a microfiltration assembly; the input end of the device is connected with the output end of the second body, and the output end of the device is connected with the input end of the hydrogen storage material of the first body, and the device is used for screening the circulating hydrogen storage material.
2. The reaction device according to claim 1, wherein a hydrogen inlet and a first hydrogen outlet are provided in the height direction of the first body; and a second hydrogen outlet is formed in the second body.
3. The reaction apparatus of claim 1 or 2, further comprising a plurality of sampling windows dispersed on the connection lines of the first body and the second body.
4. According to claimThe reaction apparatus of claim 3, wherein the liquid organic material is an aromatic liquid organic material; the solid alloy powder is a rare earth series AB 5 At least one of a zirconium alloy, a titanium alloy, a vanadium alloy and a magnesium alloy.
5. The reaction device of claim 4, wherein the first body further comprises a first fill port and a second fill port; the first filling port is used for inputting the liquid organic material into the first body; the second charging port is used for inputting the solid alloy powder into the first body.
6. A reaction apparatus as claimed in claim 3 wherein the first and second bodies are each provided with a drain for discharging the hydrogen storage material after use.
7. A hydrogen storage control method, characterized by comprising the steps of:
assembling the reaction device of any one of claims 1-6;
introducing a flow of liquid organic material and solid alloy powder into the first body until it circulates steadily in the first body and the second body;
heating the first body and the second body, and then introducing hydrogen with certain pressure into the first body;
periodically monitoring the particle size of the solid alloy powder, and adjusting the mass ratio of the liquid organic material to the solid alloy powder and the flow rate of the liquid organic material according to the particle size change of the solid alloy powder.
8. The method of claim 7, wherein the step of determining the position of the probe is performed,
initial volumetric flow rate Q of the liquid organic material 0 ＝V*TOF；
Wherein Q is 0 The unit is L/min; v is the first body and theThe sum of the volumes of the second body is expressed as L; TOF is the space velocity of the hydrogen storage reaction and the hydrogen release reaction of the liquid organic material and the solid alloy powder, and the unit is min -1 ；
TOF＝k*m l /m g ；
Wherein k is the speed constant of the hydrogen storage reaction and the hydrogen release reaction of the liquid organic material and the solid alloy powder, and the unit is min -1 ；m l The unit is kg of the mass of the liquid organic material; m is m g The unit is kg for the mass of the solid alloy powder.
9. The method of claim 7, wherein the method of adjusting the mass ratio of liquid organic material to the solid alloy powder according to the change in particle size of the solid alloy powder comprises:
when the particle diameter d of the solid alloy powder m With an initial particle diameter d 0 The ratio of (2) is 1:20-50, the particle diameter d is used 0 The solid alloy powder replacement particle diameter of d m The solid alloy powder of (2) has a particle diameter d m The mass percentage of the solid alloy powder to be replaced is 20-80% based on the mass of the solid alloy powder;
obtaining a relation between particle size of solid alloy powder in the newly formed hydrogen storage material and space velocity and flow of liquid organic material;
TOF adjustment of ＝f(d)；
Wherein TOF is Adjustment of Space velocity in min for hydrogen storage reaction and hydrogen release reaction of the newly formed hydrogen storage material -1 ；
Q=f (d), Q being the volumetric flow rate of the liquid organic material in L/min;
Q adjustment of ＝V*TOF Adjustment of ＝V*f(d)
Wherein Q is Adjustment of The unit is L/min for the volume flow of the liquid organic material after adjustment; TOF (time of flight) Adjustment of Space velocity in min for hydrogen storage reaction and hydrogen release reaction of the newly formed hydrogen storage material -1 The method comprises the steps of carrying out a first treatment on the surface of the V is the first body and theThe sum of the volumes of the second body is given by L.
10. The method of claim 9, wherein Q is defined Adjustment of >2Q 0 In the time-course of which the first and second contact surfaces,
wherein Q is Adjustment of For the volume flow of the regulated liquid organic material; q (Q) 0 An initial volumetric flow rate for the liquid organic material; m is m l An initial mass of the liquid organic material; m is m g An initial mass of the solid alloy powder; m is m l-tone The mass of the liquid organic material is regulated according to the particle size of the solid alloy powder; m is m g-shape regulating device The mass of the solid alloy powder is regulated according to the particle size of the solid alloy powder.
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