CN112713284B - Hydrogen supply system of hydrogen fuel cell and heat utilization method - Google Patents
Hydrogen supply system of hydrogen fuel cell and heat utilization method Download PDFInfo
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- CN112713284B CN112713284B CN201911019791.1A CN201911019791A CN112713284B CN 112713284 B CN112713284 B CN 112713284B CN 201911019791 A CN201911019791 A CN 201911019791A CN 112713284 B CN112713284 B CN 112713284B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04052—Storage of heat in the fuel cell system
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
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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
- Y02E60/50—Fuel cells
Abstract
The invention discloses a hydrogen supply system of a hydrogen fuel cell and a heat utilization method, wherein the hydrogen supply system of the hydrogen fuel cell comprises: a storage tank I (1) and a reactor (3); a heat exchanger (2); a separation tank (4); a tank II (5); a buffer tank (6); a hydrogen fuel cell (7); an energy storage device (8) and an energy usage unit (9). The invention combines the hydrogen fuel cell and the dehydrogenation and energy storage device of the hydrogen storage material, takes the change of the working condition of the fuel cell and the like into consideration, stores the redundant energy of the fuel cell by using the flexible energy storage device and supplies the redundant energy to the dehydrogenation reaction process of the hydrogen storage material, and has the advantages of simple flow, convenient operation and high energy utilization rate.
Description
Technical Field
The invention belongs to the technical field of hydrogen fuel cells, and particularly relates to a hydrogen supply system of a hydrogen fuel cell and a high-efficiency heat utilization method of the system.
Background
Hydrogen energy has been widely spotlighted as a representative of green sustainable new energy. In the beginning of the 21 st century, hydrogen energy development plans were made in china, the united states, japan, canada, the european union, and the like, and related studies were pursued. Hydrogen energy applications include hydrogen gas production, storage, transportation, and application links, where safe storage and high purity hydrogen gas supply are critical and difficult. Hydrogen-fueled vehicles are the primary route to hydrogen energy applications, and the development of safe storage and hydrogen gas supplies suitable for hydrogen-fueled vehicles is a prerequisite for large-scale application of hydrogen energy.
At present, the hydrogen storage technology mainly comprises physical hydrogen storage, adsorption hydrogen storage and chemical hydrogen storage. Physical hydrogen storage technology has met the requirements of vehicles, but its high requirements on equipment and harsh operating conditions have made the contradiction between performance and efficiency of this technology increasingly prominent. The adsorption hydrogen storage and the chemical hydrogen storage are the key points of the current research, and certain research results are obtained, but the requirements of the vehicle-mounted hydrogen storage technology are different. The organic liquid hydrogen storage technology (organic liquid mainly comprises methyl cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydro-azoethylcarbazole, perhydro-carbazole and the like) in chemical hydrogen storage realizes hydrogen energy storage through catalytic addition and dehydrogenation reversible reaction, the reaction in the process is reversible, a reactant product can be recycled, the hydrogen storage amount is relatively high (about 60-75kg H2/m3, the mass fraction is 6-8%), the indexes specified by the International energy agency and the United states department of energy (DOE) are met, long-distance transportation is carried out in an organic liquid form, or the problem of uneven distribution of energy can be solved, the requirements of green chemistry are really met, and the organic liquid hydrogen storage technology has a strong application prospect.
The organic liquid hydrogen storage technology generates hydrogen through dehydrogenation reaction for supplying to a fuel cell, and the dehydrogenation reaction is endothermic reaction and needs to supply energy. CN201510167958.4 provides a liquid hydrogen source material hydrogen supply reaction system based on a hydrogen fuel cell, in which the liquid hydrogen source material firstly enters a pipeline heat transfer device arranged outside the hydrogen fuel cell, and after transferring heat generated by the hydrogen fuel cell to a reaction kettle through a heat transfer device, the liquid hydrogen source material enters the reaction kettle to perform dehydrogenation reaction. Wherein the heating device of the reaction kettle is a waste heat exchanger, an electric heating device, a microwave heating device, an electromagnetic heating device or a chemical reaction heating device. The heating device outside the reaction kettle is an electric heating device, a microwave heating device or a chemical reaction heat release and exchange device. CN201610059961.9 provides a fuel cell hydrogen supply system with high efficiency heat energy utilization, which includes a dehydrogenation reactor and a hydrogen fuel heat utilization device, wherein the dehydrogenation reactor is used for generating hydrogen gas from liquid hydrogen source material through dehydrogenation reaction, part of the hydrogen gas generated by the dehydrogenation reactor is provided to the hydrogen fuel cell through a pipeline, and part of the hydrogen gas is provided to the hydrogen fuel heat utilization device; the hydrogen fuel heat utilization device is used for converting part of hydrogen generated by the dehydrogenation reaction kettle and the purge tail gas of the hydrogen fuel cell into heat energy and supplying the heat energy to the dehydrogenation reaction kettle.
The hydrogen fuel cell and the method for utilizing heat of the hydrogen supply system thereof provided by the prior art either directly supply heat to the hydrogen supply system through the outside or convert hydrogen into heat energy to supply heat to the hydrogen supply system, and the methods have the problems of more heat exchange times, large energy loss, low system heat utilization rate and the like.
Disclosure of Invention
In view of the problems of more heat exchange times, large energy loss, low system heat utilization rate and the like in the conventional hydrogen fuel cell hydrogen supply system and utilization method, the invention provides a hydrogen fuel cell hydrogen supply system and a high-efficiency heat utilization method.
In order to solve the above technical problem, a first aspect of the present invention provides a hydrogen fuel cell hydrogen supply system, wherein the hydrogen fuel cell hydrogen supply system includes:
a storage tank I (1) for storing a hydrogen storage material;
a reactor 3 receiving the hydrogen storage material from the storage tank I (1) and performing a dehydrogenation reaction;
the heat exchanger 2 is used for exchanging heat between the hydrogen storage material in the storage tank I (1) and the material at the outlet of the reactor 3 before the hydrogen storage material in the storage tank I (1) enters the reactor 3;
a separation tank 4 for separating hydrogen gas and dehydrogenation material generated from the dehydrogenation reaction in the reactor 3;
a storage tank II 5 for storing the dehydrogenation material separated from the separation tank 4;
a buffer tank (6) for storing the hydrogen gas separated from the separation tank 4 and feeding the hydrogen gas to the hydrogen fuel cell 7;
a hydrogen fuel cell 7;
an energy storage device 8 for storing a part of the electric energy generated by the hydrogen fuel cell 7 and supplying the energy to the reactor 3; and an energy usage unit 9 that receives, uses, or converts the output power portion of the hydrogen fuel cell 7.
In the embodiment of the present invention, the energy storage device 8 is a micro energy storage device, the energy storage device 8 is preferably a micro battery and/or a micro super capacitor, the energy storage device 8 is further preferably a planar micro battery and/or a micro super capacitor, and the energy storage device 8 is further preferably one or more of a lithium ion micro battery, a zinc ion micro battery, an ionic liquid gel-based micro super capacitor and a lithium ion micro capacitor.
In another aspect, the present invention further provides a heat utilization method of the hydrogen supply system of the hydrogen fuel cell, wherein the method includes:
1) the hydrogen storage material in the storage tank I (1) and the material at the outlet of the reactor 3 are sent into the reactor 3 filled with dehydrogenation catalyst after heat exchange by the heat exchanger 2;
2) under the action of a dehydrogenation catalyst, the hydrogen storage material is subjected to dehydrogenation reaction in the reactor 3 to generate dehydrogenation material and hydrogen;
3) feeding the dehydrogenation material and the hydrogen into a separation tank 4 for separation to obtain the hydrogen and the dehydrogenation material, wherein the dehydrogenation material is fed into a storage tank II 5, the hydrogen is fed into a buffer tank 6, and the hydrogen in the buffer tank 6 is fed into a hydrogen fuel cell 7;
4) a part of the power generated by the hydrogen fuel cell 7 is output to an energy output and use unit (9) using the energy of the hydrogen fuel cell, a part of the power is stored in an energy storage device 8, and the energy storage device 8 provides energy for the reactor 3;
the energy storage device 8 controls the external output power of the hydrogen fuel cell 7 through current, and ensures that the output power fluctuates within the requirement (for example, plus or minus 2%) of the energy use unit 9; the hydrogen fuel cell 7 can feed back the power of the energy using unit 9, the feedback refers to the feedback that the hydrogen fuel cell 7 can feed back the power of the using unit 9 to the energy storage device 8 in real time so as to control the output of the hydrogen fuel cell 7 to the energy storage device 8, and meanwhile, the energy storage device 8 can control the output power to the reactor 3 according to the feedback power of the energy using unit 9. The feedback and control described above can be readily implemented by conventional control systems in the art with the various parts of the system being self-contained.
In the embodiment of the present invention, in order to better improve the energy utilization rate, preferably, when the external output power of the hydrogen fuel cell 7 is 100 parts (based on the system power), the output power of the hydrogen fuel cell 7 to the end of the energy using unit 9 is 68-82 parts, the energy stored in the energy storage device 8 is 18-32 parts, and the energy storage device 8 outputs 10-25 parts of power to the reactor 3 according to the power of the energy using unit 9 fed back (the difference between the power of the energy using unit 9 and a set value, if the difference exceeds the set value, the power is not output to the energy using unit 9, if the difference is lower than the set value, the power is output to the energy using unit 9 to the set value); when the external output power of the fuel cell 7 exceeds 100 parts, the energy storage device 8 outputs 10-15 parts of power to the reactor 3, and the energy stored by the energy storage device 8 is 25-32 parts.
In the embodiment of the present invention, the energy storage device 8 may be a micro energy storage device, the energy storage device 8 is preferably a micro battery and/or a micro super capacitor, the energy storage device 8 is further preferably a planar micro battery and/or a micro super capacitor, and the energy storage device 8 is further preferably one or more of a lithium ion micro battery, a zinc ion micro battery, an ionic liquid gel-based micro super capacitor, and a lithium ion micro capacitor; the energy density of the energy storage device 8 can be selected according to actual needs, for example, the energy density can be 0.2w/kg-20w/kg, and the energy efficiency is 85% -95%. The redundant energy generated by the fuel cell is stored in the flexible energy storage device which can change the shape and be independently disassembled and assembled, and the energy storage device receives the energy supplied by the hydrogen fuel cell and outputs power to the outside on the one hand, so that the heat utilization efficiency of the system is obviously improved.
In the embodiment of the invention, the energy storage device 8 outputs the stored energy to the reactor 3 as electric energy, and the output power accounts for 40-60% of the stored power. The energy storage means 8 can supply the stored energy to the reactor 3 as electrical energy output by acting on the reactor 3 by means of electrical heating.
In the embodiment of the invention, the selection of the buffer tank needs to be adapted to the parameters of the hydrogen fuel cell, for example, the pressure of the buffer tank 6 can be maintained at 1-3 MPa; the amount of hydrogen delivered by the buffer tank 6 to the hydrogen fuel cell 7 may differ from the demand by ± 5%.
In the embodiment of the present invention, the hydrogen storage material may be various hydrogen storage materials conventionally used in the art, and preferably, the hydrogen storage material is an organic liquid hydrogen storage material, for example, the hydrogen storage material is one or more of cyclohexane, methylcyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole, perhydrophenanthrene, perhydroanthracene, perhydrocarbazole or their derivatives, a component for cutting a segment from petroleum or distillate oil of petroleum, and a hydrogenated material of a cut component.
In an embodiment of the present invention, the dehydrogenation catalyst may include, in parts by weight: (a) 0.1-5 parts of one or more alloys selected from elements in group VIII of the periodic table, (b) 75-99 parts of a carrier; the element in the VIII group is Pt, Pd, Rh or Ir; the carrier is a carbon carrier, and the carbon carrier is a carbon nano tube, graphene or graphite alkyne. Preferably, in the present invention, the carbon support is treated with halogen.
The hydrogen supply system of the hydrogen fuel cell, provided by the invention, stores redundant energy of the fuel cell by using the flexible energy storage device by combining the hydrogen fuel cell and the dehydrogenation and energy storage device of the hydrogen storage material in consideration of the change of the working condition of the fuel cell and the like, and supplies the redundant energy to the dehydrogenation reaction process of the hydrogen storage material.
Drawings
The invention will be described below with reference to the accompanying drawings.
Fig. 1 is a schematic diagram of a hydrogen supply system and material/energy flow for a hydrogen fuel cell in accordance with an embodiment of the present invention.
Wherein: 1 is a storage tank I; 2 is a heat exchanger; 3 is a reactor; 4 is a separating tank; 5 is a storage tank II; 6 is a buffer tank; 7 is a hydrogen fuel cell; 8 is an energy storage device; and 9 is an energy using unit.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. However, before the present invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
In the present invention, the raw materials or components used may be commercially or conventionally prepared unless otherwise specified.
Example 1
As shown in fig. 1, a hydrogen fuel cell hydrogen supply system includes: a storage tank I1 for storing hydrogen storage materials; a reactor 3 for receiving the hydrogen storage material from the storage tank I1 and carrying out dehydrogenation reaction; the heat exchanger 2 is used for exchanging heat between the hydrogen storage material in the storage tank I1 and the material at the outlet of the reactor 3 before the hydrogen storage material in the storage tank I1 enters the reactor 3; a separation tank 4 for separating hydrogen gas and dehydrogenation material generated from the dehydrogenation reaction in the reactor 3; a storage tank II 5 for storing the dehydrogenation material separated from the separation tank 4; a buffer tank 6 for storing the hydrogen gas separated from the separation tank 4 and supplying the hydrogen gas to the hydrogen fuel cell 7; a hydrogen fuel cell 7; the energy storage device 8 is a planar micro-battery for storing a part of the electric energy generated by the hydrogen fuel cell 7 and supplying the energy to the reactor 3; and an energy usage unit 9 that receives, uses, or converts the output power portion of the hydrogen fuel cell 7.
The heat utilization method of the hydrogen supply system of the hydrogen fuel cell comprises the following steps:
1) the methyl cyclohexane in the storage tank I1 and the material at the outlet of the reactor 3 are sent into the reactor 3 filled with dehydrogenation catalyst after heat exchange by the heat exchanger 2;
2) under the action of dehydrogenation catalyst, hydrogen storage material is dehydrogenated in reactor 3 to produce dehydrogenation material (toluene and dehydrogenation distillate) and hydrogen gas; the energy required by the dehydrogenation process is provided by the planar micro battery of the energy storage device 8;
3) sending the dehydrogenation material and the hydrogen into a separation tank 4 for separation to obtain gaseous hydrogen and liquid dehydrogenation material, wherein the dehydrogenation material is sent into a storage tank II 5, the hydrogen is sent into a buffer tank 6, and the hydrogen in the buffer tank 6 is sent into a hydrogen fuel cell 7;
4) 80 parts of power generated by the hydrogen fuel cell 7 is externally output to an energy output using unit 9 using energy of the hydrogen fuel cell, and 20 parts of power is stored in an energy storage device 8. When 11kg of methylcyclohexane is consumed in the fuel tank 1, the power output from the energy usage unit 9 to the outside is 10 kw.
Wherein the energy density of the energy storage device 8 is 10w/kg, and the energy efficiency is 95%. The selection of the buffer tank needs to be adapted to the parameters of the hydrogen fuel cell, and the pressure of the buffer tank 6 is maintained at 2 MPa; the amount of hydrogen delivered by the buffer tank 6 to the hydrogen fuel cell 7 may differ from the demand by ± 5%. The dehydrogenation catalyst is Pt/graphite alkyne.
Example 2
As shown in fig. 1, a hydrogen fuel cell hydrogen supply system includes: a storage tank I1 for storing hydrogen storage materials; a reactor 3 for receiving the hydrogen storage material from the storage tank I1 and carrying out dehydrogenation reaction; the heat exchanger 2 is used for exchanging heat between the hydrogen storage material in the storage tank I1 and the material at the outlet of the reactor 3 before the hydrogen storage material in the storage tank I1 enters the reactor 3; a separation tank 4 for separating hydrogen and dehydrogenation material generated from the dehydrogenation reaction in the reactor 3; a storage tank II 5 for storing the dehydrogenation material separated from the separation tank 4; a buffer tank 6 for storing the hydrogen gas separated from the separation tank 4 and supplying the hydrogen gas to the hydrogen fuel cell 7; a hydrogen fuel cell 7; the energy storage device 8 flattens the micro-battery and is used for storing part of the electric energy generated by the hydrogen fuel cell 7 and providing energy for the reactor 3; and an energy usage unit 9 that receives, uses, or converts a portion of the output power of the hydrogen fuel cell 7.
The heat utilization method of the hydrogen supply system of the hydrogen fuel cell comprises the following steps:
1) the methyl cyclohexane in the storage tank I1 and the material at the outlet of the reactor 3 are sent into the reactor 3 filled with dehydrogenation catalyst after heat exchange by a heat exchanger 2;
2) under the action of dehydrogenation catalyst, hydrogen storage material is dehydrogenated in reactor 3 to produce dehydrogenation material (toluene and dehydrogenation distillate) and hydrogen gas; the energy required by the dehydrogenation process is provided by the planar micro battery of the energy storage device 8;
3) feeding the dehydrogenation material and the hydrogen into a separation tank 4 for separation to obtain gaseous hydrogen and liquid dehydrogenation material, wherein the dehydrogenation material is fed into a storage tank II 5, the hydrogen is fed into a buffer tank 6, and the hydrogen in the buffer tank 6 is fed into a hydrogen fuel cell 7;
4) 68 parts of power generated by the hydrogen fuel cell 7 is externally output to an energy output using unit 9 using energy of the hydrogen fuel cell, and 32 parts of power are stored in the energy storage device 8. When the fuel tank 1 consumes 11kg of methylcyclohexane, the power output from the energy usage unit 9 to the outside is 8 kw.
Wherein the energy density of the energy storage device 8 is 20w/kg, and the energy efficiency is 95%. The selection of the buffer tank needs to be adapted to the parameters of the hydrogen fuel cell, and the pressure of the buffer tank 6 is maintained at 1 MPa; the amount of hydrogen delivered by the buffer tank 6 to the hydrogen fuel cell 7 may differ from the demand by ± 5%. The dehydrogenation catalyst is Pt/graphite alkyne.
Example 3
As shown in fig. 1, a hydrogen fuel cell hydrogen supply system includes: a storage tank I1 for storing a hydrogen storage material; a reactor 3 for receiving the hydrogen storage material from the storage tank I1 and carrying out dehydrogenation reaction; the heat exchanger 2 is used for exchanging heat between the hydrogen storage material in the storage tank I1 and the material at the outlet of the reactor 3 before the hydrogen storage material in the storage tank I1 enters the reactor 3; a separation tank 4 for separating hydrogen gas and dehydrogenation material generated from the dehydrogenation reaction in the reactor 3; a storage tank II 5 for storing the dehydrogenation material separated from the separation tank 4; a buffer tank 6 for storing the hydrogen gas separated from the separation tank 4 and supplying the hydrogen gas to the hydrogen fuel cell 7; a hydrogen fuel cell 7; the energy storage device 8 is a planar micro-battery for storing a part of the electric energy generated by the hydrogen fuel cell 7 and supplying the energy to the reactor 3; and an energy usage unit 9 that receives, uses, or converts the output power portion of the hydrogen fuel cell 7.
The heat utilization method of the hydrogen supply system of the hydrogen fuel cell comprises the following steps:
1) the methyl cyclohexane in the storage tank I1 and the material at the outlet of the reactor 3 are sent into the reactor 3 filled with dehydrogenation catalyst after heat exchange by the heat exchanger 2;
2) under the action of dehydrogenation catalyst, hydrogen storage material is dehydrogenated in reactor 3 to produce dehydrogenation material (toluene and dehydrogenation distillate) and hydrogen gas; the energy required by the dehydrogenation process is provided by the planar micro battery of the energy storage device 8;
3) feeding the dehydrogenation material and the hydrogen into a separation tank 4 for separation to obtain gaseous hydrogen and liquid dehydrogenation material, wherein the dehydrogenation material is fed into a storage tank II 5, the hydrogen is fed into a buffer tank 6, and the hydrogen in the buffer tank 6 is fed into a hydrogen fuel cell 7;
4) 75 parts of the power generated by the hydrogen fuel cell 7 is externally output to an energy output using unit 9 using the energy of the hydrogen fuel cell, and 25 parts of the power is stored in the energy storage device 8. When the fuel tank 1 consumes 11kg of methylcyclohexane, the power output from the energy usage unit 9 to the outside is 11 kw.
Wherein the energy density of the energy storage device 8 is 15w/kg, and the energy efficiency is 85%. The selection of the buffer tank needs to be adapted to the parameters of the hydrogen fuel cell, and the pressure of the buffer tank 6 is maintained at 3 MPa; the amount of hydrogen delivered by the buffer tank 6 to the hydrogen fuel cell 7 may differ from the demand by ± 5%. The dehydrogenation catalyst is Pt/graphite alkyne.
Example 4
As shown in fig. 1, a hydrogen fuel cell hydrogen supply system includes: a storage tank I1 for storing hydrogen storage materials; a reactor 3 for receiving the hydrogen storage material from the storage tank I1 and carrying out dehydrogenation reaction; the heat exchanger 2 is used for exchanging heat between the hydrogen storage material in the storage tank I1 and the material at the outlet of the reactor 3 before the hydrogen storage material in the storage tank I1 enters the reactor 3; a separation tank 4 for separating hydrogen gas and dehydrogenation material generated from the dehydrogenation reaction in the reactor 3; a storage tank II 5 for storing the dehydrogenation material separated from the separation tank 4; a buffer tank 6 for storing the hydrogen gas separated from the separation tank 4 and supplying the hydrogen gas to the hydrogen fuel cell 7; a hydrogen fuel cell 7; the energy storage device 8 is a planar micro-battery for storing a part of the electric energy generated by the hydrogen fuel cell 7 and supplying the energy to the reactor 3; and an energy usage unit 9 that receives, uses, or converts the output power portion of the hydrogen fuel cell 7.
The heat utilization method of the hydrogen supply system of the hydrogen fuel cell comprises the following steps:
1) the methyl cyclohexane in the storage tank I1 and the material at the outlet of the reactor 3 are sent into the reactor 3 filled with dehydrogenation catalyst after heat exchange by a heat exchanger 2;
2) under the action of dehydrogenation catalyst, hydrogen storage material is dehydrogenated in reactor 3 to produce dehydrogenation material (toluene and dehydrogenation distillate) and hydrogen gas; the energy required by the dehydrogenation process is provided by the planar micro-battery of the energy storage device 8;
3) feeding the dehydrogenation material and the hydrogen into a separation tank 4 for separation to obtain gaseous hydrogen and liquid dehydrogenation material, wherein the dehydrogenation material is fed into a storage tank II 5, the hydrogen is fed into a buffer tank 6, and the hydrogen in the buffer tank 6 is fed into a hydrogen fuel cell 7;
4) 90 parts of power generated by the hydrogen fuel cell 7 is externally output to an energy output using unit 9 using energy of the hydrogen fuel cell, and 10 parts of power is output to the fuel cell by the energy storage device 8. When 11kg of methylcyclohexane is consumed in the fuel tank 1, the power output from the energy usage unit 9 to the outside is 10 kw.
Wherein the energy density of the energy storage device 8 is 10w/kg, and the energy efficiency is 95%. The selection of the buffer tank needs to be adapted to the parameters of the hydrogen fuel cell, and the pressure of the buffer tank 6 is maintained at 2 MPa; the amount of hydrogen delivered by the buffer tank 6 to the hydrogen fuel cell 7 may differ from the demand by ± 5%. The dehydrogenation catalyst is Pt/graphite alkyne.
Example 5
As shown in fig. 1, a hydrogen fuel cell hydrogen supply system includes: a storage tank I1 for storing hydrogen storage materials; a reactor 3 for receiving the hydrogen storage material from the storage tank I1 and carrying out dehydrogenation reaction; the heat exchanger 2 is used for exchanging heat between the hydrogen storage material in the storage tank I1 and the material at the outlet of the reactor 3 before the hydrogen storage material in the storage tank I1 enters the reactor 3; a separation tank 4 for separating hydrogen gas and dehydrogenation material generated from the dehydrogenation reaction in the reactor 3; a storage tank II 5 for storing the dehydrogenation material separated from the separation tank 4; a buffer tank 6 for storing the hydrogen gas separated from the separation tank 4 and supplying the hydrogen gas to the hydrogen fuel cell 7; a hydrogen fuel cell 7; the energy storage device 8 is a planar micro-battery for storing a part of the electric energy generated by the hydrogen fuel cell 7 and supplying the energy to the reactor 3; and an energy usage unit 9 that receives, uses, or converts a portion of the output power of the hydrogen fuel cell 7.
The heat utilization method of the hydrogen supply system of the hydrogen fuel cell comprises the following steps:
1) the methyl cyclohexane in the storage tank I1 and the material at the outlet of the reactor 3 are sent into the reactor 3 filled with dehydrogenation catalyst after heat exchange by a heat exchanger 2;
2) under the action of dehydrogenation catalyst, hydrogen storage material is dehydrogenated in reactor 3 to produce dehydrogenation material (toluene and dehydrogenation distillate) and hydrogen gas; the energy required by the dehydrogenation process is provided by the planar micro battery of the energy storage device 8;
3) feeding the dehydrogenation material and the hydrogen into a separation tank 4 for separation to obtain gaseous hydrogen and liquid dehydrogenation material, wherein the dehydrogenation material is fed into a storage tank II 5, the hydrogen is fed into a buffer tank 6, and the hydrogen in the buffer tank 6 is fed into a hydrogen fuel cell 7;
4) 60 parts of power generated by the hydrogen fuel cell 7 is externally output to an energy output using unit 9 using the energy of the hydrogen fuel cell, 40 parts of power are stored in the energy storage device 8, and meanwhile, the energy storage device 8 outputs 8 parts of power to the dehydrogenation unit 3. When the fuel tank 1 consumes 11kg of methylcyclohexane, the power output from the energy usage unit 9 to the outside is 9 kw.
Wherein the energy density of the energy storage device 8 is 10w/kg, and the energy efficiency is 95%. The selection of the buffer tank needs to be adapted to the parameters of the hydrogen fuel cell, and the pressure of the buffer tank 6 is maintained at 2 MPa; the amount of hydrogen delivered by the buffer tank 6 to the hydrogen fuel cell 7 may differ from the demand by ± 5%. The dehydrogenation catalyst is Pt/graphite alkyne.
Comparative example 1
A hydrogen fuel cell hydrogen supply system comprising: a storage tank I1 for storing hydrogen storage materials; a reactor 3 for receiving the hydrogen storage material from the storage tank I1 and carrying out dehydrogenation reaction; the heat exchanger 2 is used for exchanging heat between the hydrogen storage material in the storage tank I1 and the material at the outlet of the reactor 3 before the hydrogen storage material in the storage tank I1 enters the reactor 3; a separation tank 4 for separating hydrogen gas and dehydrogenation material generated from the dehydrogenation reaction in the reactor 3; a storage tank II 5 for storing the dehydrogenation material separated from the separation tank 4; a buffer tank 6 for storing the hydrogen gas separated from the separation tank 4 and supplying the hydrogen gas to the hydrogen fuel cell 7; a hydrogen fuel cell 7; the energy storage device 8 flattens the micro-battery and is used for storing part of the electric energy generated by the hydrogen fuel cell 7; and an energy usage unit 9 that receives, uses, or converts the output power portion of the hydrogen fuel cell 7.
The heat utilization method of the hydrogen supply system of the hydrogen fuel cell comprises the following steps:
1) the methyl cyclohexane in the storage tank I1 and the material at the outlet of the reactor 3 are sent into the reactor 3 filled with dehydrogenation catalyst after heat exchange by the heat exchanger 2;
2) under the action of dehydrogenation catalyst, hydrogen storage material is dehydrogenated in reactor 3 to produce dehydrogenation material (toluene and dehydrogenation distillate) and hydrogen gas; the energy required by the dehydrogenation process is provided by external electric energy;
3) sending the dehydrogenation material and the hydrogen into a separation tank 4 for separation to obtain gaseous hydrogen and liquid dehydrogenation material, wherein the dehydrogenation material is sent into a storage tank II 5, the hydrogen is sent into a buffer tank 6, and the hydrogen in the buffer tank 6 is sent into a hydrogen fuel cell 7;
4) 90 parts of power generated by the hydrogen fuel cell 7 is externally output to an energy output using unit 9 using energy of the hydrogen fuel cell, and 10 parts of power is stored in an energy storage device 8. When the fuel tank 1 consumes 11kg of methylcyclohexane, the power output from the energy usage unit 9 to the outside is 6 kw.
Wherein the energy storage device, the buffer tank and the dehydrogenation catalyst are all the same as in example 1.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (13)
1. A hydrogen fuel cell hydrogen supply system, characterized by comprising:
a storage tank I (1) for storing a hydrogen storage material;
a reactor (3) for receiving the hydrogen storage material from the storage tank I (1) and carrying out dehydrogenation reaction;
the heat exchanger (2) is used for exchanging heat between the hydrogen storage material in the storage tank I (1) and the material at the outlet of the reactor (3) before the hydrogen storage material in the storage tank I (1) enters the reactor (3);
a separation tank (4) for separating hydrogen and dehydrogenation material from the dehydrogenation reaction in the reactor (3);
a storage tank II (5) for storing the dehydrogenated material separated from the separation tank (4);
a buffer tank (6) for storing the hydrogen gas separated from the separation tank (4) and delivering the hydrogen gas to a hydrogen fuel cell (7);
a hydrogen fuel cell (7);
an energy storage device (8) for storing a portion of the electrical energy generated by the hydrogen fuel cell (7) and providing energy to the reactor (3); and an energy usage unit (9) receiving, using or converting the output power portion of the hydrogen fuel cell (7),
the energy storage device (8) controls the external output power of the hydrogen fuel cell (7) through current so as to ensure that the output power fluctuates within +/-2% of the requirement of the energy using unit (9); the hydrogen fuel cell (7) can feed back the power of the energy using unit (9) to control the output of the hydrogen fuel cell (7) to the energy storage device (8), and the energy storage device (8) can control the output power of the reactor (3) according to the fed back power of the energy using unit (9).
2. A hydrogen fuel cell hydrogen supply system according to claim 1, characterized in that the energy storage device (8) is a planarized micro-battery and/or a micro-supercapacitor.
3. The hydrogen fuel cell hydrogen supply system according to claim 2, characterized in that the energy storage device (8) is one or more of a lithium ion micro battery, a zinc ion micro battery, an ionic liquid gel based micro supercapacitor, a lithium ion micro capacitor.
4. A heat utilization method of a hydrogen fuel cell hydrogen supply system, characterized in that the method is realized by the hydrogen fuel cell hydrogen supply system according to any one of claims 1 to 3, comprising:
1) the hydrogen storage material in the storage tank I (1) and the material at the outlet of the reactor (3) are sent into the reactor (3) filled with dehydrogenation catalyst after heat exchange by the heat exchanger (2);
2) under the action of a dehydrogenation catalyst, the hydrogen storage material is subjected to dehydrogenation reaction in the reactor (3) to generate dehydrogenation material and hydrogen;
3) feeding the dehydrogenation material and the hydrogen into a separation tank (4) for separation to obtain the hydrogen and the dehydrogenation material, wherein the dehydrogenation material is fed into a storage tank II (5), the hydrogen is fed into a buffer tank (6), and the hydrogen in the buffer tank (6) is fed into a hydrogen fuel cell (7);
4) a part of the power generated by the hydrogen fuel cell (7) is externally output to an energy output using unit 9 using the energy of the hydrogen fuel cell, and a part of the power is stored in an energy storage device (8), wherein the energy storage device (8) provides energy for the reactor (3);
the energy storage device (8) controls the external output power of the hydrogen fuel cell (7) through current, and ensures that the output power fluctuates within +/-2% of the requirement of the energy using unit (9); the hydrogen fuel cell (7) can feed back the power of the energy using unit (9) to control the output of the hydrogen fuel cell (7) to the energy storage device (8), and the energy storage device (8) can control the output power of the reactor (3) according to the fed back power of the energy using unit (9).
5. The heat utilization method according to claim 4, wherein when the external output power of the hydrogen fuel cell (7) is 100 parts, the output power of the hydrogen fuel cell (7) to the energy utilization unit (9) is 68-82 parts, the energy stored in the energy storage device (8) is 18-32 parts, and the energy storage device (8) outputs 10-25 parts of power to the reactor (3) according to the feedback power of the energy utilization unit (9); when the external output power of the hydrogen fuel cell (7) exceeds 100 parts, the energy storage device (8) outputs 10-15 parts of power to the reactor (3), and the energy stored by the energy storage device (8) is 25-32 parts.
6. The heat utilization method according to claim 4 or 5, wherein the energy storage device (8) is a micro battery and/or a micro supercapacitor; the energy density of the energy storage device (8) is 0.2-20 w/kg, and the energy efficiency is 85-95%.
7. The method according to claim 6, characterized in that the energy storage device (8) is a planarized micro battery and/or a micro supercapacitor.
8. The heat utilization method according to claim 7, wherein the energy storage device (8) is one or more of a lithium ion micro battery, a zinc ion micro battery, an ionic liquid gel based micro supercapacitor, a lithium ion micro capacitor.
9. The heat utilization method according to claim 4 or 5, wherein the energy storage device (8) supplies the stored energy to the reactor (3) as electrical energy output, the output power being 40-60% of the stored power.
10. The heat utilization method according to claim 4 or 5, wherein the pressure of the buffer tank (6) is maintained at 1 to 3 MPa; the difference between the amount of the hydrogen delivered to the hydrogen fuel cell (7) by the buffer tank (6) and the required amount is +/-5%.
11. The heat utilization method according to claim 4 or 5, wherein the hydrogen storage material is one or more of cyclohexane, methylcyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole, perhydrophenanthrene, perhydroanthracene, perhydrocarbazole or derivatives thereof, a component obtained by cutting a segment from petroleum or distillate oil of petroleum, and a hydrogenated material obtained by hydrogenating the cut component.
12. The heat utilization method of claim 4 or 5, wherein the dehydrogenation catalyst comprises, in parts by weight: (a) 0.1-5 parts of one or more alloys selected from elements in group VIII of the periodic table, (b) 75-99 parts of a carrier; the element in the VIII group is Pt, Pd, Rh or Ir; the carrier is a carbon carrier, and the carbon carrier is a carbon nano tube, graphene or graphite alkyne.
13. The heat utilization method of claim 12, wherein the carbon support is treated with a halogen.
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| CN104979574A (en) * | 2015-04-10 | 2015-10-14 | 江苏氢阳能源有限公司 | Liquid-state hydrogen source material hydrogen supply reaction system based on hydrogen fuel cell |
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| CN104979574A (en) * | 2015-04-10 | 2015-10-14 | 江苏氢阳能源有限公司 | Liquid-state hydrogen source material hydrogen supply reaction system based on hydrogen fuel cell |
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