WO2016161955A1 - 一种液态氢源材料的脱氢反应系统 - Google Patents

一种液态氢源材料的脱氢反应系统 Download PDF

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Publication number
WO2016161955A1
WO2016161955A1 PCT/CN2016/078759 CN2016078759W WO2016161955A1 WO 2016161955 A1 WO2016161955 A1 WO 2016161955A1 CN 2016078759 W CN2016078759 W CN 2016078759W WO 2016161955 A1 WO2016161955 A1 WO 2016161955A1
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Prior art keywords
liquid
hydrogen
source material
reaction
liquid hydrogen
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PCT/CN2016/078759
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English (en)
French (fr)
Inventor
程寒松
孙雁龙
管一龙
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江苏氢阳能源有限公司
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Priority claimed from CN201510167935.3A external-priority patent/CN104973567B/zh
Priority claimed from CN201510167881.0A external-priority patent/CN104975987B/zh
Priority claimed from CN201510167977.7A external-priority patent/CN104971675B/zh
Priority claimed from CN201510167978.1A external-priority patent/CN104975988B/zh
Priority claimed from CN201510167958.4A external-priority patent/CN104979574B/zh
Priority claimed from CN201510318905.8A external-priority patent/CN104973568B/zh
Priority claimed from CN201510919949.6A external-priority patent/CN106861559A/zh
Priority claimed from CN201510922921.8A external-priority patent/CN106882765A/zh
Priority claimed from CN201610059961.9A external-priority patent/CN107017420A/zh
Priority to EP16776130.3A priority Critical patent/EP3281912A4/en
Priority to US15/557,746 priority patent/US10586993B2/en
Application filed by 江苏氢阳能源有限公司 filed Critical 江苏氢阳能源有限公司
Priority to JP2018500846A priority patent/JP6506468B2/ja
Publication of WO2016161955A1 publication Critical patent/WO2016161955A1/zh

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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
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • 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
    • C01B3/0015—Organic compounds; Solutions thereof
    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • 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
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
    • B60L58/30—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C01B2203/067—Integration with other chemical processes with fuel cells the reforming process taking place in the fuel cell
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1252—Cyclic or aromatic hydrocarbons
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells

Definitions

  • the invention relates to the technical field of organic liquid hydrogen storage, in particular to a dehydrogenation system of a liquid hydrogen source material at normal temperature and normal pressure.
  • Hydrogen energy technologies include the scale preparation, storage and transportation of hydrogen, high-efficiency use, and the construction of supporting infrastructure. Storage and transportation are safe and effective. Hydrogen energy is one of the most critical technologies. At present, the industry mainly uses liquefied hydrogen at -253 ° C or high-pressure hydrogen at 350-700 atmospheres. The energy consumption required for high-pressure hydrogen or liquefied hydrogen technology and its application is more than 20 times that of hydrogen production. There are safety hazards such as leakage or high pressure in the hydrogen storage tank. If the hydrogen molecules can be adsorbed on a certain carrier, the safe storage under normal temperature and normal pressure can be realized, and when the hydrogen can be controlled to be released under mild conditions, the hydrogen energy can be effectively and safely used.
  • liquid organic hydrogen storage technology based on normal temperature and pressure.
  • the liquid organic hydrogen storage technology developed can achieve the hydrogen absorption/desorption cycle under mild conditions, but the high melting point of the hydrogen storage carrier is an important defect in the solid state at normal temperature; Japan is currently developing traditional organic materials based on toluene and the like.
  • Hydrogen storage technology but the dehydrogenation temperature is too high (greater than 300 ° C), and there are also problems with byproduct poisoning fuel cells. Therefore, the scale application of these two hydrogen storage technologies is restricted.
  • a dehydrogenation reaction system of a liquid hydrogen source material which comprises:
  • a storage device for storing a liquid hydrogen source material and a liquid hydrogen storage carrier
  • a gas-liquid separator for separating a product hydrogen and a liquid hydrogen storage carrier after dehydrogenating a liquid hydrogen source material.
  • the liquid hydrogen storage carrier comprises at least two different hydrogen storage components, the hydrogen storage component is an unsaturated aromatic hydrocarbon or a heterocyclic unsaturated compound, and at least one hydrogen storage component is a low melting point compound, and a low melting point compound The melting point is lower than 80 ° C;
  • the storage device is provided with a storage space for respectively storing a liquid hydrogen source material and a liquid hydrogen storage carrier;
  • the reaction kettle is a plate type, a tube type, a plug type, a tower type or the like;
  • the liquid hydrogen source material is input into the reaction vessel through a pump through a pump, and a dehydrogenation reaction of the liquid hydrogen source material is performed in the reaction vessel, and the generated hydrogen gas is sent to the buffer tank, and the liquid hydrogen storage carrier generated after dehydrogenation is simultaneously Transfer back to the storage device.
  • the heating device of the reaction kettle is a waste heat exchanger, an electric heating device, an electromagnetic heating device, a chemical reaction heating device or a microwave heating device, and a preheating device is disposed outside the input pipe, and a liquid hydrogen source in the storage device
  • the material is directly introduced into the reaction vessel by preheating to carry out a dehydrogenation reaction.
  • the reaction vessel is a thin plate reactor or a thin tube tubular reactor, which is inserted into a support.
  • the bracket has a multi-layer structure, and is provided with a total liquid inlet pipe, a total liquid outlet pipe and a total air outlet pipe, and each layer is provided with a liquid inlet pipe, a liquid outlet pipe, a gas outlet pipe, a heating device and a reaction kettle bayonet.
  • the reaction kettle is provided with a liquid inlet port, a liquid outlet port and an air outlet port; when the reaction kettle is inserted into the reaction vessel bayonet of the bracket, the inlet and outlet of the reaction kettle and the hydrogen outlet are respectively connected with the total inlet pipe and the total outlet pipe of the support And the total outlet pipe is turned on.
  • the inlet pipe, the outlet pipe, and the outlet pipe are provided with a communication valve, and the inlet port, the outlet port and the outlet port of the reaction kettle are respectively connected to the liquid inlet pipe and the liquid outlet pipe through the communication valve. Divide the trachea.
  • the reactor heating device is a waste heat exchanger, an electric heating device, a microwave heating device, an electromagnetic heating device or a chemical reaction heating device.
  • the reaction vessel comprises an insulation layer and one or more reaction units, the insulation layer is wrapped outside the reaction unit;
  • the reaction unit comprises a reaction section and a heating section, the reaction section is internally filled with a catalyst, and the heating section a heating device is disposed therein;
  • the reaction units are sequentially connected, the reaction raw materials are introduced from the inlet of the reaction vessel, and the endothermic reaction is sequentially performed through each reaction unit, and the reaction product is discharged from the outlet of the reaction vessel;
  • a support frame the reaction unit is fixed on the support frame, and the reaction units and the reaction section and the heating section are separated by a partition;
  • the layer is a mesh, membrane or molecular sieve.
  • the dehydrogenation reaction system is further provided with a first pressure sensor for detecting the reactor pressure
  • a second pressure sensor for detecting the pressure of the buffer tank
  • a level gauge for detecting the liquid level position in the gas-liquid separator
  • a controller for collecting signals of the first and second pressure sensors and the liquid level meter and transmitting a control signal for controlling flow of the raw materials and reaction products in the reaction device when the pre-set conditions are met And the start and stop of the dehydrogenation reaction.
  • the controller controls the flow rate of the raw materials and the reaction products in the reaction device and the start and stop of the dehydrogenation reaction by controlling the input pump disposed at the outlet of the storage device, the hydrogen boosting pump disposed at the gas outlet of the gas-liquid separator, and being disposed in the gas
  • the first valve of the liquid outlet of the liquid separator and the start and stop of the heating device are specifically: when the second pressure sensor detects that the pressure of the buffer tank is lower than the first set value during normal operation, the controller controls the input pump to improve
  • the liquid hydrogen source material is sent to the flow rate of the reaction vessel, and the liquid hydrogen source material is subjected to dehydrogenation reaction in the reaction vessel to increase the hydrogen generation rate to increase the pressure of the buffer tank; and the first pressure sensor detects that the pressure of the reaction kettle is higher than the set value.
  • the controller controls to start the hydrogen booster pump, the internal pressure of the reactor is lower than the set pressure; when the second pressure sensor detects that the pressure in the buffer tank is higher than the second set value, the controller controls to close the input pump and the reaction kettle.
  • the external heating device stops the reaction kettle; when the liquid level gauge detects that the liquid level position in the gas-liquid separator is higher than the set value, the controller controls to open the first Door, so that the liquid hydrogen source material within the gas-liquid separator flows into the storage device.
  • the buffer tank is connected to a hydrogen fuel cell.
  • a heat conducting device is disposed between the reaction vessel and the heating device, and the heat conducting device is connected to the pipeline heat transfer device disposed outside the hydrogen fuel cell through a pipeline, and the heat conducting medium flowing through the heat conducting device and the pipeline heat transfer device is a storage liquid hydrogen source material.
  • the storage device is connected to the pipeline heat transfer device, and the heat conduction device is connected to the reaction kettle through the input pipe, and the liquid hydrogen source material first enters the pipeline heat transfer device disposed outside the hydrogen fuel cell, and the heat generated by the hydrogen fuel cell is transmitted to the reaction kettle through the heat conduction device. After that, the reactor is further introduced to carry out a dehydrogenation reaction.
  • the heating means for heating the reaction vessel is an electric heater, an electromagnetic heater or a microwave heater.
  • the dehydrogenation reaction system further includes a storage battery for storing electric energy generated by the hydrogen fuel cell, and supplies an input pump, a preheating device, a reactor system device consumption, and an output.
  • the heating device is a hydrogen fuel heat utilization device, and the hydrogen fuel heat utilization device is connected to the reaction vessel. A part of the hydrogen gas generated by the reaction vessel and the purge tail gas of the hydrogen fuel cell are supplied to the reaction vessel by the hydrogen fuel heat utilization device being converted into heat energy.
  • the hydrogen fuel heat utilization device passes heat energy generated by hydrogen combustion through a heat transfer medium to be disposed outside the reaction vessel or The internal heat exchange tube is transferred to the dehydrogenation reactor, the heat transfer medium is a heat transfer oil or a metal salt bath; or the reaction kettle and the hydrogen fuel heat utilization device are an integral device, and the hydrogen fuel heat utilization device passes the hydrogen gas After combustion, heat is transferred to the dehydrogenation reactor.
  • the buffer tank is connected to a hydrogen internal combustion engine.
  • the dehydrogenation reaction system is also provided with an oxygen storage tank for storing oxygen, and hydrogen and oxygen are simultaneously supplied into the hydrogen internal combustion engine.
  • the hydrogen internal combustion engine is externally provided with a radiator, which is connected to the external heating device of the reaction vessel through a pipe, and transfers heat through a heat transfer medium flowing in the radiator and the heating device.
  • the storage device is connected to the radiator, and the heating device is connected to the reaction vessel through an input pipe, and the heat transfer medium is a liquid hydrogen source material.
  • the dehydrogenation system of the normal temperature and atmospheric pressure liquid hydrogen source material provided by the invention can select the size and form of the equipment in the system according to different fields of use, for example, the liquid hydrogen source material and the liquid hydrogen storage carrier after dehydrogenation.
  • the storage means of the material may be separate individual unit units or the same container separated by movable partitions for the purposes of the present invention. However, if used in a motor vehicle system, the latter, preferably the same tank, is separated by a movable or fixed partition from the viewpoint of saving the space of the motor vehicle.
  • a plate type, a tube tube type or a tower type can also be used as needed.
  • the dehydrogenation reaction device is a plug-in type from the viewpoint of saving the space of the motor vehicle, thereby saving space. According to the needs of motor vehicle power, the number of inserts can be customized. Since the hydrogen internal combustion engine can generate a temperature of up to 400 ° C during operation, the hydrogen fuel cell can also produce a temperature of 50 to 100 ° C during operation, and the liquid hydrogen source material requires 120 to 250 ° C for the dehydrogenation reaction. The liquid hydrogen source material has the specificity of maintaining stable performance at a temperature of 300 ° C.
  • the liquid hydrogen source material is used as a heat transfer medium to cool the hydrogen internal combustion engine or the hydrogen fuel cell, and the heat is transferred to the dehydrogenation reactor, and the liquid hydrogen source after the heat is transferred. The material continues to enter the reactor for the dehydrogenation chemical reaction.
  • the dehydrogenation system of the normal temperature and normal pressure liquid hydrogen source material provided by the invention is used for dehydrogenating the liquid hydrogen storage material, and the generated hydrogen is supplied to the fuel cell or the internal combustion engine to be converted into electric energy or mechanical energy for application to automobiles, power sources, Energy storage, chemical, pharmaceutical, mobile and other industrial and civil fields.
  • FIG. 1 is a schematic view showing the structure of a dehydrogenation reaction system of Example 1 of the present invention.
  • Figure 2 is a schematic view showing the structure of a dehydrogenation reaction system of Example 2 of the present invention.
  • Figure 3 is a schematic view showing the structure of a dehydrogenation reaction system of Example 4 of the present invention.
  • Figure 4 is a schematic view showing the structure of a dehydrogenation reaction system of Example 5 of the present invention.
  • Figure 5 is a schematic view showing the structure of a dehydrogenation reaction system of Example 6 of the present invention.
  • Figure 6 is a schematic view showing the structure of a dehydrogenation reaction system of Example 7 of the present invention.
  • Figure 7 is a schematic view showing the structure of a reaction vessel, a holder and a heating device of Example 8 of the present invention.
  • Figure 8 is a schematic view showing the structure of a dehydrogenation reaction system of Example 9 of the present invention.
  • Figure 9 is a schematic view showing the structure of a dehydrogenation reaction system of Example 10 of the present invention.
  • Figure 10 is a schematic view showing the structure of a dehydrogenation reaction system of Example 11 of the present invention.
  • Figure 11 is a schematic view showing the reaction vessel and the hydrogen fuel heat utilization device in an embodiment 11 of the present invention as a unitary device.
  • Figure 12 is a schematic view showing the structure of the dehydrogenation reaction system of Example 12.
  • Figure 13 is a schematic view showing the structure of a dehydrogenation heat utilization apparatus in the thirteenth embodiment.
  • Figure 14 is a schematic view of a column reactor in Example 14.
  • the liquid hydrogen storage carrier is a hydrogen storage system capable of exhibiting a liquid state at normal temperature and pressure, and includes at least two different hydrogen storage components, the hydrogen storage component being an unsaturated aromatic hydrocarbon or a heterocyclic unsaturated compound, and at least one
  • the hydrogen storage component is a low melting point compound, and the melting point of the low melting point compound is lower than 80 °C.
  • the hydrogen storage component is selected from the group consisting of heterocyclic unsaturated compounds, and the hetero atom in the heterocyclic unsaturated compound is one or more of N, S, O and P.
  • the total number of the heterocyclic ring and the aromatic ring in the heterocyclic unsaturated compound is from 1 to 20, and the total number of the hetero atoms is from 1 to 20.
  • the mass fraction of the low melting point compound is 5 to 95% with respect to the total mass of the liquid hydrogen storage system.
  • liquid hydrogen storage system further includes a hydrogenation additive, and the hydrogenation additive is a polar solvent and/or a non-polar solvent.
  • the hydrogenation additive is added in an amount of 0.1 to 10 mL per gram of the hydrogen storage component.
  • the different hydrogen storage components are respectively selected from the group consisting of benzene, toluene, ethylbenzene, o-xylene, p-xylene, styrene, phenylacetylene, anthracene, naphthalene, anthracene, aniline, carbazole, N-methylcarbazole , N-ethylcarbazole, N-n-propyl carbazole, N-isopropylcarbazole, N-n-butylcarbazole, anthracene, N-methylhydrazine, N-ethylhydrazine, N a group consisting of -propyl hydrazine, quinoline, isoquinoline, pyridine, pyrrole, furan, benzofuran, thiophene, pyrimidine and imidazole and derivatives thereof.
  • the polar solvent is selected from the group consisting of ethanol, methanol, diethyl ether, methyl ether, acetonitrile, ethyl acetate, formamide, isopropanol, n-butanol, dioxane, n-butyl ether, diisopropyl ether, dichloromethane One or more of chloroform and dichloroethane.
  • non-polar solvent is selected from one or more of n-hexane, n-pentane, cyclohexane, mesitylene, carbon disulfide, petroleum ether, and carbon tetrachloride.
  • the hydrogen storage system further comprises a dehydrogenation additive selected from the group consisting of decalin, mesitylene, and stone.
  • a dehydrogenation additive selected from the group consisting of decalin, mesitylene, and stone.
  • decalin mesitylene
  • stone stone.
  • oleyl ether and phenyl ether.
  • the dehydrogenation additive is added in an amount of 0.1 to 10 mL per gram of the hydrogen storage component.
  • the liquid hydrogen storage carrier is subjected to a hydrogenation chemical reaction under the action of a hydrogenation catalyst to form a liquid hydrogen source material, and the liquid hydrogen source material is subjected to a dehydrogenation chemical reaction under the action of a dehydrogenation catalyst to be reduced to a liquid hydrogen storage carrier.
  • a storage device for storing a liquid hydrogen source material and a liquid hydrogen storage carrier may be a storage tank or other form, and the volume may be a micro or a vehicle or a large storage tank.
  • the storage device may be provided with a space for respectively storing the liquid hydrogen source material and the liquid hydrogen storage carrier: a first storage chamber and a second storage chamber, and the first and second storage chambers are respectively provided with an input port and an output port.
  • the output port of the first storage chamber is provided with an input pump, and the liquid hydrogen source material is input into the reaction kettle by the operation of the input pump.
  • the storage device may also be a storage tank for storing a liquid hydrogen source material and a liquid hydrogen storage carrier, respectively, each of which is provided with an input port and an output port.
  • the preheating device may be disposed outside the input pipe connecting the pump and the reaction kettle, and the preheating device may be electrically heated or other forms to preheat the liquid hydrogen source material input to the reaction vessel to 150 °C.
  • the reactor may be in the form of a plate, a tube, a column or the like, and is internally filled with a dehydrogenation catalyst.
  • the reaction vessel is provided with a heating device for heating the reaction vessel, and the heating device may be a waste heat exchanger, a microwave heating device, an electric heating device, a heat utilization device or other heating device, and the heat utilization device uses hydrogen, natural gas, liquefied gas, gasoline.
  • the liquid hydrogen source material can be subjected to a dehydrogenation reaction at a temperature of 120 to 250 °C.
  • the dehydrogenation process is to input the liquid hydrogen source material stored in the storage device into the reaction kettle by a pump, and the liquid hydrogen source material reacts to release hydrogen gas and generate liquid hydrogen storage under the action of the dehydrogenation catalyst at 120 to 250 ° C under 0 to 1 MPa atmospheric pressure.
  • the carrier, hydrogen is sent to the buffer tank, and the liquid hydrogen storage carrier is sent back to the storage device.
  • the reactor may also be a thin-plate reactor or a thin-layer tubular reactor, and the reactor is inserted into the stent.
  • the bracket has a multi-layer structure, and is provided with a total liquid inlet pipe, a total liquid outlet pipe and a total gas outlet pipe, and each layer is provided with a liquid inlet pipe, a liquid outlet pipe, a gas outlet pipe, a heating device and a reaction kettle bayonet.
  • the reaction kettle is provided with a liquid inlet port, a liquid outlet port and an air outlet port; when the reaction kettle is inserted into the reaction vessel bayonet of the bracket, the inlet and outlet of the reactor and the hydrogen outlet are respectively connected to the total inlet pipe, the total outlet pipe and the total outlet of the support.
  • the trachea is turned on.
  • the inlet valve, the outlet pipe, and the outlet pipe are provided with a communication valve, and the inlet port, the outlet port and the outlet port of the reaction kettle are respectively connected to the liquid inlet pipe, the liquid outlet pipe, and the outlet through the communication valve. trachea.
  • the reactor heating device may employ various heating devices such as a waste heat exchanger, an electric heating device, a microwave heating device, an electromagnetic heating device, or a chemical reaction heating device.
  • the plate reactor is a thin layer structure. In order to ensure the efficiency of the catalytic reaction, the thickness of the reactor cannot be thick to avoid the existence of a gradient, resulting in unstable reaction and low efficiency.
  • the reaction vessel can be inserted into the stent as needed, and the stent is of a multi-layer structure and can be inserted into a single or multiple reactors.
  • Each layer of the stent is divided into a liquid inlet tube, a liquid outlet tube and a minute
  • the communication valve of the air outlet pipe is in a connected state when connecting the liquid inlet port, the liquid outlet port and the air outlet port of the reaction vessel, otherwise it is closed.
  • the heating device is disposed at the front end of the reaction vessel, or the number of the heating devices exceeds one.
  • the heating devices are disposed at a uniform distance from each other outside the reaction vessel, and the heating device heats the reaction vessel in stages.
  • the reaction vessel is required to maintain a temperature of 120 to 250 ° C to maintain the dehydrogenation reaction of the liquid hydrogen source material. Therefore, a heating device is disposed on the support, and the heating device is disposed outside the reactor or located The front end of the reactor. Since the dehydrogenation reaction of the liquid hydrogen source material is the most efficient under the segment heating condition, it is preferred that the number of heating devices exceeds one, and the heating devices are disposed at a uniform distance from each other outside the reaction vessel, and the heating device heats the reactor in stages. .
  • a modular design can also be employed in the tower reactor, the reactor comprising an insulating layer and one or more reaction units, the insulation layer being wrapped around the exterior of all of the reaction units.
  • the reaction unit includes a reaction section and a heating section, the inside of the reaction section is filled with a catalyst, and a heating device is disposed in the heating section.
  • the reaction units are sequentially connected, and the reaction raw materials are introduced from the inlet of the reaction vessel, and an endothermic reaction is sequentially carried out through each reaction unit, and the reaction product is discharged from the outlet of the reaction vessel.
  • a support frame is disposed in the reaction kettle, and the reaction unit is fixed on the support frame, and the reaction units are separated from each other between the reaction section and the heating section by a partition.
  • the compartment is a mesh, membrane or molecular sieve.
  • the heating device at this time is an electric heater, an infrared heater, an electromagnetic heater, a microwave heater or a duct heater.
  • the reactor may be provided with a temperature controller for controlling the temperature of each heating device.
  • the catalyst is in the form of particles, and the filling method is a fixed bed, a fluidized bed or the like.
  • the thermal insulation layer comprises an inner layer of the thermal insulation layer, an outer layer of the thermal insulation layer and an insulation material filled between the inner and outer layers, a vacuum is applied between the inner layer of the thermal insulation layer and the outer layer of the thermal insulation layer, and the inner layer of the thermal insulation layer is coated with a heat radiation reflective coating or a heat of winding. Radiation reflective material.
  • the reactants are first heated to a suitable temperature through the heating section, and then reacted under the action of the catalyst.
  • the number of reaction units, the heat retention mode and the heating mode can be selected according to the actual needs of the reaction, and the heating equipment is separately controlled, as needed. Control the actual heating temperature and heat of each heating layer separately, add heat exchanger according to the actual situation, greatly improve the utilization of energy, and make the reaction more complete and controllable, and avoid local overheating during heating. And the side reaction produced. After the reaction, the gas-liquid with heat is exchanged with the raw material of the inlet, which can effectively improve the energy utilization rate.
  • the liquid hydrogen source material is catalytically decomposed into hydrogen and liquid hydrogen storage carrier in the reaction kettle, and the reaction product is first separated into the gas-liquid separation device for separation, and the generated hydrogen gas is sent to the buffer tank, and the liquid hydrogen storage carrier is transported back to the storage liquid storage.
  • the space of the hydrogen carrier is
  • the liquid hydrogen source material can be controlled during dehydrogenation to obtain a stable amount of hydrogen. It can be arranged in the dehydrogenation system: a first pressure sensor for detecting the pressure of the reactor; a second pressure sensor for detecting the pressure of the buffer tank; and a liquid level gauge for detecting the liquid level position in the gas-liquid separator; For collecting the first and second pressure sensors to And the signal of the liquid level meter transmits a control signal for controlling the flow rate of the raw materials and the reaction products in the reaction equipment and the start and stop of the dehydrogenation reaction when the conditions according to the preset conditions are satisfied.
  • a preheater for preheating the liquid hydrogen source material is disposed between the storage tank and the reaction kettle. Also included is a pressure regulator valve and a second valve disposed between the buffer tank and the hydrogen utilization device.
  • the controller is a PLC, a microcontroller or a DCS.
  • the storage device is connected to the preheater through an input pump, the preheater is connected to the reaction kettle, the reaction kettle is connected to the gas-liquid separator, the gas outlet of the gas-liquid separator is connected to the buffer tank, the liquid outlet is connected to the storage tank, the buffer tank and the hydrogen fuel cell are connected. Connected.
  • the reactor was equipped with a heating device and the entire system was controlled by PLC.
  • a first pressure sensor is provided in the reaction vessel for detecting the reactor pressure.
  • a second pressure sensor is provided in the buffer tank for detecting the buffer tank pressure.
  • a liquid level gauge is provided in the gas-liquid separator for detecting the liquid level position in the gas-liquid separator. The signals of the first and second pressure sensors and the level gauge are sent to the PLC, and when the predetermined conditions are met, the control signal is sent to control the input pump disposed on the storage tank and the preheater line, and the gas is disposed in the gas-liquid separator.
  • the hydrogen booster pump at the outlet, the first valve disposed at the liquid outlet of the gas-liquid separator, and the start and stop of the heating device.
  • a pressure regulator valve and a second valve between the buffer tank and the hydrogen utilization device.
  • the PLC controls the input pump to increase the flow rate of the liquid hydrogen source material to the preheater, and the liquid hydrogen source material is preheated. It is sent to a reaction vessel filled with a dehydrogenation catalyst, and a liquid hydrogen source material is subjected to a dehydrogenation reaction in the reaction vessel to increase the hydrogen generation rate to increase the pressure of the buffer tank. Hydrogen is supplied to the hydrogen fuel cell through the regulator valve and the second valve.
  • the PLC controls to start the hydrogen booster pump, so that the internal pressure of the reactor is lower than the set pressure.
  • the PLC controls to close the input pump and the heating device outside the reactor to stop the reactor.
  • the PLC controls to open the first valve, and the liquid hydrogen storage carrier in the gas-liquid separator flows into the storage tank.
  • the liquid hydrogen source material and the liquid hydrogen storage carrier are stored in a storage tank, and the storage tank is provided with a space for respectively storing the liquid hydrogen source material and the liquid hydrogen storage carrier: a first storage chamber and a second storage chamber, and two storage chambers Interval with movable partitions.
  • the second valve is opened, and the hydrogen stored in the buffer tank is started by being input into the hydrogen fuel cell.
  • the second pressure sensor of the buffer tank detects that the pressure in the tank is lower than the first set value
  • the input is increased through the PLC.
  • the pump inputs the flow rate of the liquid hydrogen source material, and the liquid hydrogen source material is sent to the preheater through the transfer pump, preheated to 100-250 ° C, and then enters the reaction kettle, and dehydrogenation is carried out under the action of a dehydrogenation catalyst at 120-250 ° C.
  • the reaction product enters the gas-liquid separator.
  • the hydrogen booster pump is started by the PLC control, and the hydrogen in the gas-liquid separator is stored in the buffer tank through the hydrogen booster pump, buffering
  • the pressure in the tank is 0.03 to 1 MPa, and the pressure in the reactor is kept at normal pressure or micro-negative pressure.
  • Hydrogen is delivered to the hydrogen fuel cell through a pressure regulating valve at a pressure of 0.03 to 0.06 MPa.
  • the liquid hydrogen storage carrier in the gas-liquid separator reaches a set liquid level, and the opening degree of the first valve is controlled by the PLC to be transported back to the second storage chamber of the storage tank.
  • the flow rate of the input pump is increased by the PLC control, and the flow rate of the liquid hydrogen source material for performing the dehydrogenation reaction is increased.
  • the heating device that turns off the input pump and the outside of the reactor is controlled by the PLC to stop the dehydrogenation reaction.
  • Hydrogen can be delivered from the buffer tank to the hydrogen fuel cell for conversion to electrical energy.
  • the heating device of the reaction vessel is a waste heat exchanger, an electric heating device, a microwave heating device, an electromagnetic heating device, or a chemical reaction heating device.
  • a preheating device may also be provided between the hydrogen source material storage tank and the reaction kettle. The liquid hydrogen source material in the storage tank passes through the preheating and directly enters the reaction vessel for dehydrogenation reaction.
  • a heat conducting device is disposed between the reaction vessel and the heating device, and the heat conducting device is connected to the pipeline heat transfer device disposed outside the hydrogen fuel cell through a pipeline, and the heat conducting medium flowing through the heat conducting device and the pipeline heat transfer device is a liquid hydrogen source material.
  • the liquid hydrogen source material first enters the pipeline heat transfer device disposed outside the hydrogen fuel cell, and the heat generated by the hydrogen fuel cell is conducted to the reaction vessel through the heat conduction device, and then enters the reaction vessel for dehydrogenation reaction.
  • the hydrogen fuel cell can generate a temperature of 50 to 100 ° C during operation, and the liquid hydrogen source material requires 120 to 250 ° C for the dehydrogenation reaction.
  • the heat energy generated by the hydrogen fuel cell can be fully utilized.
  • a battery When hydrogen energy is converted into electric energy, a battery may be provided for storing electric energy generated by the hydrogen fuel cell, and supplying system equipment consumption such as a pump and a heating device and output.
  • the liquid hydrogen source material stored in the storage device is sent to the preheating device through the input pump for heating, and then enters the reaction vessel to generate hydrogen and liquid hydrogen storage carrier under a certain temperature and catalyst condition, and the product is separated in the gas-liquid separator.
  • the liquid hydrogen storage carrier is transported back to the storage device, and the hydrogen gas enters the buffer tank.
  • the dehydrogenation reaction can generate a certain pressure, and the buffer tank is connected to the dehydrogenation reactor to have a certain pressure, and the hydrogen gas is converted into electric energy into the hydrogen fuel cell.
  • the electric energy part is used for supplying the system equipment such as the pump and the heating device, and the rest of the output; during the use, part of the electric energy is stored in the battery, and can be used for the next start.
  • the dehydrogenation reactor in the dehydrogenation system needs to work. If heat is required, if the hydrogen generated by the hydrogen supply system is generated by the fuel cell and supplied to the dehydrogenation system by electricity, the rated power of the fuel cell will be increased and the hydrogen gas will be burned at the same net output power. The heat utilization rate is higher. Therefore, the heating device for heating the reactor may be a hydrogen fuel heat utilization device, and the hydrogen fuel heat utilization device is connected to the reaction vessel, and part of the hydrogen gas generated by the reaction vessel and the purge tail gas of the hydrogen fuel cell are converted into heat energy by the hydrogen fuel heat utilization device. Reactor.
  • the hydrogen fuel heat utilization device transfers the heat energy generated by the hydrogen combustion to the dehydrogenation reaction tank through the heat transfer medium through the heat transfer medium disposed outside or inside the reaction vessel, and the heat conduction medium is a heat conduction oil or a metal salt bath; or the dehydrogenation heat utilization device
  • the dehydrogenation reactor and the hydrogen fuel heat utilization device are an integral device, and the hydrogen fuel heat utilization device transmits heat energy to the dehydrogenation reactor by burning hydrogen gas, thereby improving energy utilization.
  • Hydrogen can be transferred from the buffer tank to the hydrogen internal combustion engine to mechanical energy. Since the liquid hydrogen source material can provide more hydrogen per unit volume than the high-pressure hydrogen storage technology and the solid hydrogen storage technology, the space for storing the liquid hydrogen source material can be greatly reduced, and thus can be applied in the fields of automobiles, trains, ships, and the like. Allow enough space to install an oxygen tank. In the hydrogen energy vehicle using the hydrogen internal combustion engine in the prior art, since there is not enough space to install the oxygen tank, the hydrogen inside the hydrogen internal combustion engine directly reacts with the oxygen in the air, and the nitrogen in the air reacts with the oxygen at a high temperature to generate nitrogen and oxygen.
  • the compound, the oxynitride is a carcinogen.
  • the oxygen content in the air is relatively low, and nitrogen oxides are more likely to be produced.
  • the invention adopts direct oxygen to enter the hydrogen internal combustion engine for reaction, does not generate nitrogen oxides, does not need to be equipped with an exhaust gas treatment device, and greatly saves cost, is more energy-saving and environmentally friendly.
  • a hydrogen radiator is disposed outside the hydrogen internal combustion engine, and is connected to an external heating device of the reaction vessel through a pipe.
  • the storage device is connected to the radiator, and the heating device is connected to the reaction vessel through an input pipe, and the heat transfer medium is a liquid hydrogen source material.
  • the storage device is a storage tank, and the liquid hydrogen source material and the liquid hydrogen storage carrier are respectively stored in different storage tanks 101, and each storage tank is provided with an input port and an output port respectively, and the liquid hydrogen source is stored therein.
  • the output port of the material storage tank is provided with a pump 102, and an external heating device 103 is disposed outside the input pipe connecting the pump and the reaction kettle, and the preheating device is an electric heating device.
  • the liquid hydrogen source material is introduced into the reaction vessel 104 by the operation of the pump.
  • the reaction vessel was a column reactor and was internally filled with a dehydrogenation catalyst.
  • the liquid hydrogen source material is decomposed into hydrogen and a liquid hydrogen storage carrier in the reaction vessel, and the hydrogen storage carrier is transported back to the space in which the hydrogen storage carrier is stored.
  • Hydrogen is delivered to the buffer tank 105 and then from the buffer tank to the hydrogen fuel cell 106. Outside the reactor
  • the electric heating device 107 is provided to maintain the temperature of the reaction vessel at 120 to 250 °C.
  • the storage device is an in-vehicle storage tank, and the storage tank is provided with a space for respectively storing a liquid hydrogen source material liquid and a hydrogen storage carrier: a first storage chamber 108 and a second storage chamber 109, first and second storage chambers.
  • Each setting has an input port and an output port.
  • the output port of the first storage compartment is provided with a pump 102, and the input pipe connected to the pump and the reaction kettle is provided with a preheating device 103, and the preheating device is an electric heating device powered by the battery.
  • the liquid hydrogen source material is introduced into the reaction vessel 104 by the operation of the pump.
  • the reaction vessel was a plate reactor and was internally filled with a dehydrogenation catalyst.
  • the liquid hydrogen source material is decomposed into hydrogen and a liquid hydrogen storage carrier in the reaction vessel, and the liquid hydrogen storage carrier is transported back to the second storage chamber in which the liquid hydrogen storage carrier is stored.
  • Hydrogen is delivered to the buffer tank 105 and then from the buffer tank to the hydrogen internal combustion engine 110.
  • a microwave heating device 111 is provided outside the reactor to maintain the temperature of the reactor at 120 to 250 °C.
  • the storage device is a micro storage tank, and the storage tank is provided with a space for respectively storing the liquid hydrogen source material and the hydrogen storage carrier: a first storage chamber and a second storage chamber, and the first and second storage chambers are respectively provided with an input port and an output port.
  • the output of the first storage compartment is provided with a pump.
  • the liquid hydrogen source material is input into the pipeline heat transfer device provided outside the hydrogen internal combustion engine by the pump, and the heat generated by the hydrogen internal combustion engine is transmitted to the reaction kettle through the heating device, and then enters the reaction vessel for dehydrogenation reaction, and the reaction kettle is a tubular reactor.
  • the interior is filled with a dehydrogenation catalyst.
  • the liquid hydrogen source material is decomposed into hydrogen and a hydrogen storage carrier in the reaction vessel, and the hydrogen storage carrier is transported back to the space in which the hydrogen storage carrier is stored.
  • Hydrogen is delivered to the buffer tank and then from the buffer tank to the hydrogen internal combustion engine.
  • An electric heating device was provided outside the reactor to maintain the temperature of the reactor at 120 to 250 °C.
  • the dehydrogenation reaction system comprises: a storage tank for storing a liquid hydrogen source material and a liquid hydrogen storage carrier, a reaction vessel 104 for dehydrogenating the liquid hydrogen source material, and a buffer for storing hydrogen gas.
  • a tank 105 for storing a liquid hydrogen source material and a liquid hydrogen storage carrier
  • a reaction vessel 104 for dehydrogenating the liquid hydrogen source material
  • a buffer for storing hydrogen gas.
  • a tank 105 for heating the reaction vessel
  • a hydrogen fuel cell 106 for heating the reaction vessel.
  • the storage tank for storing the liquid hydrogen source material and the liquid hydrogen storage carrier is provided with a space for respectively storing the liquid hydrogen source material and the liquid hydrogen storage carrier: the first storage chamber 108 and the second storage chamber 109, and the two storage chambers are spaced apart by Active partition 112.
  • the first and second storage compartments are each provided with an input port and an output port.
  • the output port of the first storage compartment is provided with a pump 102.
  • the reaction vessel may be a plate reactor equipped with a dehydrogenation catalyst.
  • the plate reactor can be insert-type and can increase the number of inserts according to the demand of the car.
  • a preheating device 103 is disposed outside the input pipe connecting the pump and the reaction vessel for the purpose of improving the efficiency and speed of the dehydrogenation reaction in a specific application process.
  • the preheating device can be electrically heated or other forms, and the liquid hydrogen source input into the reaction kettle The material was preheated to 150 °C.
  • the liquid hydrogen source material is decomposed into hydrogen and a liquid hydrogen storage carrier in the reaction vessel, and the liquid hydrogen storage carrier is transported back to the hydrogen storage tank to store the second storage chamber of the liquid hydrogen storage carrier. Since the two storage compartments are separated by a movable partition, after the liquid hydrogen source material is output, the space of the first storage compartment is reduced, and the space of the second storage compartment is increased, which can be used for storing the liquid storage that is transported back. Hydrogen carrier helps save space. After the liquid hydrogen source material is dehydrogenated to form a liquid hydrogen storage carrier, the liquid hydrogen storage carrier can be withdrawn through the output port of the second storage chamber, and the liquid hydrogen source material is poured into the input port of the first storage chamber.
  • the hydrogen produced in the reactor is sent to a buffer tank and then to a hydrogen fuel cell.
  • the reactor needs a temperature of 120 to 250 ° C to maintain the dehydrogenation reaction of the liquid hydrogen source material. Therefore, a heating device is provided outside the reactor, and the heating device is an electric heater.
  • the hydrogen storage device inputs the liquid hydrogen source material into the reaction kettle through the input pipe through the pump, and the hydrogen generated by the dehydrogenation of the liquid hydrogen source material is sent to the buffer tank, and the liquid hydrogen storage carrier generated after the dehydrogenation is transported back to the hydrogen storage tank.
  • the hydrogen in the tank and the buffer tank is sent to the hydrogen fuel cell, and the chemical energy is converted into electric energy, and the electric energy is converted into kinetic energy to drive the engine.
  • the dehydrogenation reaction system includes: a storage tank for storing the liquid hydrogen source material and the liquid hydrogen storage carrier, a reaction vessel 104 for dehydrogenating the liquid hydrogen source material, and a buffer tank for storing hydrogen. 105.
  • the storage tank for storing the liquid hydrogen source material and the liquid hydrogen storage carrier is provided with a space for respectively storing the liquid hydrogen source material and the liquid hydrogen storage carrier: the first storage chamber 108 and the second storage chamber 109, and the two storage chambers are spaced apart by Active partition 112.
  • the first and second storage compartments are each provided with an input port and an output port, and the output port of the first storage compartment is provided with a pump 102 through which the liquid hydrogen source material is output through the operation of the pump.
  • a heat conducting device is disposed between the reaction vessel and the heating device. The heat conducting device is connected to the pipeline heat transfer device 115 disposed outside the hydrogen fuel cell through a pipeline, and the heat conducting medium flowing through the heating device and the pipeline heat transfer device is a storage liquid hydrogen source material.
  • the liquid hydrogen source material is input into the pipeline heat transfer device disposed outside the hydrogen fuel cell by the pump, and the heat generated by the hydrogen fuel cell is transmitted to the reaction kettle through the heating device, and then enters the reaction vessel for dehydrogenation reaction, and the reaction kettle is tubular
  • the reaction vessel was internally filled with a dehydrogenation catalyst.
  • the liquid hydrogen source material is catalytically decomposed in the reaction vessel, and the product is sent to a gas-liquid separation device for separation into hydrogen and a liquid hydrogen storage carrier, and the liquid hydrogen storage carrier is transported back to the space where the hydrogen storage carrier is stored.
  • Hydrogen is delivered to the buffer tank and then from the buffer tank to the hydrogen fuel cell.
  • a microwave heating device is provided outside the reactor to maintain the temperature of the reactor at 120 to 250 °C.
  • the hydrogen storage tank for storing the liquid hydrogen source material and the liquid hydrogen storage carrier is provided with a space for storing the liquid hydrogen source material and the liquid hydrogen storage carrier, respectively: the first storage chamber 108 and the second storage chamber 109.
  • the two storage compartments are separated by a movable partition 112.
  • the first and second storage compartments are each provided with an input port and an output port, and the output port of the first storage compartment is provided with a pump 102 through which the liquid hydrogen source material is input into the reaction vessel 104 through the operation of the pump.
  • the reaction vessel was a plate reactor equipped with a dehydrogenation catalyst.
  • a preheating device 103 is disposed outside the input pipe connecting the pump and the reaction kettle, and the preheating device uses an electric heater to preheat the liquid hydrogen source material input to the reaction vessel to 150 °C.
  • the liquid hydrogen source material is catalytically decomposed in the reaction vessel, and the liquid hydrogen storage carrier is transported back to the second storage chamber of the hydrogen storage tank to store the liquid hydrogen storage carrier. Since the two storage compartments are separated by a movable partition, after the liquid hydrogen source material is output, the space of the first storage compartment is reduced, and the space of the second storage compartment is increased, which can be used for storing the liquid storage that is transported back. Hydrogen carrier helps save space. After the liquid hydrogen source material is dehydrogenated to form a liquid hydrogen storage carrier, the liquid hydrogen storage carrier can be withdrawn through the output port of the second storage chamber, and the liquid hydrogen source material is poured into the input port of the first storage chamber.
  • the hydrogen gas generated in the reactor is sent to the buffer tank 105, and then enters the hydrogen internal combustion engine 110, while the hydrogen gas and the oxygen in the oxygen storage tank 116 are supplied to the hydrogen internal combustion engine by the pump at a mass ratio of 1:8, and the hydrogen and oxygen are carried out in the hydrogen internal combustion engine.
  • the conversion of chemical energy to mechanical energy drives the operation of transportation equipment such as cars or boats.
  • the hydrogen internal combustion engine will generate a high temperature of about 400 ° C, and the reactor needs a temperature of 120 to 250 ° C to maintain the dehydrogenation reaction of the liquid hydrogen source material. Therefore, a heat exchange device is disposed outside the hydrogen internal combustion engine and the reaction vessel: externally disposed outside the hydrogen internal combustion engine The radiator 117 and the heater 118 disposed outside the reactor.
  • the radiator and the heater are connected by a pipeline, and the heat transfer medium cools the hydrogen internal combustion engine and heats the reaction vessel. Through heat exchange, the heat energy generated by the hydrogen internal combustion engine can be fully utilized.
  • a pump is provided on the pipeline to ensure the flow of the heat transfer medium between the radiator and the heater.
  • the hydrogen storage tank for storing the liquid hydrogen source material and the liquid hydrogen storage carrier is provided with a space for storing the liquid hydrogen source material and the liquid hydrogen storage carrier, respectively: the first storage chamber 108 and the second storage chamber 109.
  • the two storage compartments are separated by a movable partition 112.
  • the first and second storage compartments are each provided with an input port and an output port, and the output port of the first storage compartment is provided with a pump 102 through which the liquid hydrogen source material is input to the radiator 117 disposed outside the hydrogen internal combustion engine.
  • a heater 118 disposed outside the reactor is connected to the radiator through a pipeline, and the liquid hydrogen source material cools the hydrogen internal combustion engine by heat exchange and heats the reaction vessel, and finally enters the reaction vessel 104 through the inlet pipe.
  • the reaction vessel was a tubular reactor, and was internally filled with a dehydrogenation catalyst.
  • the liquid hydrogen source material is catalytically decomposed in the reaction vessel, and the product is sent to the gas-liquid separation device 113 for separation into hydrogen and a liquid hydrogen storage carrier, and the liquid hydrogen storage carrier is transported back to the hydrogen storage tank to store the second hydrogen storage carrier. Storage room.
  • the gas-liquid separation device delivers hydrogen to the buffer tank 105, After entering the hydrogen internal combustion engine 110, the hydrogen and the oxygen in the oxygen storage tank 116 are input to the hydrogen internal combustion engine by the pump at a mass ratio of 1:8. The hydrogen and oxygen are converted into chemical energy into the internal combustion engine to drive the automobile or the ship. Wait for the operation of transportation equipment.
  • the dehydrogenation system is applied to a small car.
  • the volume of the hydrogen storage tank is 60-100L, which can provide 4.5-5.8kg of hydrogen, and can travel 500 kilometers in a small car.
  • the dehydrogenation system is applied to the truck.
  • the volume of the hydrogen storage tank is 150-250L, which can provide 11.3 to 14.5 kg of hydrogen, which can drive the truck for 500 kilometers.
  • the reactor 104 is a thin-layer tubular reactor, and the number is five, and can be increased or decreased as needed.
  • the interior is filled with a dehydrogenation catalyst and an inert material.
  • the reaction kettle is provided with a liquid inlet 210, a liquid outlet 211 and an air outlet 212.
  • the reaction kettle can be inserted into the heating device in the bracket through the liquid inlet, the liquid outlet and the outlet, respectively, and the liquid inlet and the outlet. Connected to the outlet tube.
  • the heating device is an electric heating device 107, and the number of heating devices per layer is four, and the heating devices are disposed at a uniform distance from each other outside the reaction vessel, and the heating device heats the reactor in stages.
  • the liquid hydrogen source material enters the reaction tank through the total inlet pipe into the split liquid pipe, and the reaction kettle decomposes the liquid hydrogen source material into hydrogen and liquid hydrogen storage carrier under the action of the dehydrogenation catalyst at 120-250 ° C, and the hydrogen gas passes through the sub-injection pipe.
  • the outlet pipe enters the total outlet pipe and is sent to the gas storage tank, and the liquid hydrogen storage carrier enters the total liquid discharge pipe through the liquid discharge pipe and is poured into the liquid storage tank.
  • the dehydrogenation reaction system includes a storage device 101, a preheater 103, a pump 102, a reaction vessel 104, a gas-liquid separator 113, and a hydrogen fuel cell 106.
  • the storage device is used for storing the liquid hydrogen source material and the liquid hydrogen storage carrier, and is provided with a space for respectively storing the liquid hydrogen source material and the liquid hydrogen storage carrier, and the two spaces are connected by the movable partition 112.
  • the storage device stores an infusion port at one end of the liquid hydrogen source material and is connected to the preheater through a pipeline.
  • the pipeline is provided with a pump, the preheater is connected to the reaction kettle, the reaction kettle is connected to the gas-liquid separator, and the gas outlet of the gas-liquid separator is connected to the hydrogen fuel.
  • the battery and the liquid outlet connection device store and store the liquid inlet of the liquid hydrogen storage carrier.
  • the liquid hydrogen source material stored in the storage device is pumped to the preheater and heated to 150 ° C, and then enters the reaction vessel to generate hydrogen and liquid hydrogen storage carrier at 170 ° C, space velocity of 1, catalyst, and the product is in gas.
  • the liquid hydrogen storage carrier is transported back to the storage device, and the hydrogen gas is introduced into the buffer tank 105 at a pressure of about 1 to 6 bar, and then the hydrogen gas is introduced. The pressure is reduced to 0.3-0.7 bar, and the hydrogen fuel cell is converted into electric energy.
  • 25% of the generated electric energy is used for the supply of the system equipment such as the pump, the preheater and the reaction kettle, and the rest of the output; when the system is shut down, the reaction kettle still has a certain The temperature will continue to react for a period of time during which the hydrogen produced is stored in the buffer tank for use at the next startup.
  • the dehydrogenation reaction system includes a storage device 101, a preheater 103, a pump 102, a reaction vessel 104, a gas-liquid separator 113, a hydrogen fuel cell 106, and a battery 119.
  • the storage device is used for storing the liquid hydrogen source material and the liquid hydrogen storage carrier, and is provided with a space for respectively storing the liquid hydrogen source material and the liquid hydrogen storage carrier, and the two spaces are connected by a movable partition.
  • the storage device stores an infusion port at one end of the liquid hydrogen source material and is connected to the preheater through a pipeline.
  • the pipeline is provided with a pump, the preheater is connected to the reaction kettle, the reaction kettle is connected to the gas-liquid separator, and the gas outlet of the gas-liquid separator is connected to the hydrogen fuel.
  • the battery and the liquid outlet connection device store and store the liquid inlet of the liquid hydrogen storage carrier.
  • the hydrogen fuel cell is connected to the battery.
  • the liquid hydrogen source material stored in the storage device is pumped to the preheater and heated to 160 ° C, and then enters the reaction kettle to generate hydrogen and liquid hydrogen storage carrier at 190 ° C, space velocity 2, and the catalyst is in gas.
  • the liquid hydrogen storage carrier is transported back to the storage device, the hydrogen gas enters the buffer tank 105, the pressure is about 1 to 6 bar, and then the hydrogen is decompressed to 0.3-0.7 bar, and the hydrogen fuel cell is converted into electric energy, resulting in The electric energy is partially stored in the battery.
  • 20% of the electric energy of the battery is used to supply the system equipment such as the pump, the preheater and the reaction kettle, and the rest of the output; when the system is shut down, the reaction kettle still has a certain temperature and will continue to react for a while.
  • the hydrogen generated during the generation of electricity is generated by the hydrogen fuel cell and stored in the battery for use at the next startup.
  • FIG. 10 is a schematic structural view of a dehydrogenation reaction system
  • FIG. 11 is a schematic view showing the structure of a device directly combining a hydrogen fuel heat utilization device and a reaction kettle.
  • the inner layer to the outer layer are respectively a combustion reaction zone and dehydrogenation.
  • the reaction zone and the waste heat utilization zone, the combustion reaction zone is also a hydrogen fuel heat utilization device, and the dehydrogenation reaction zone is also a dehydrogenation reaction vessel.
  • Hydrogen and air are combusted in the combustion reaction zone and supplied to the inside of the dehydrogenation reaction zone, and the generated tail gas is supplied to the outside of the dehydrogenation reaction zone through the waste heat utilization zone, and the hydrogen source material is at a certain temperature and catalyst in the dehydrogenation reaction zone.
  • the reaction generates a liquid hydrogen storage carrier and hydrogen, and a part of the generated hydrogen is transported to the hydrogen fuel cell through the pipeline to be converted into electric energy, and the other part of the hydrogen and the purge exhaust gas of the hydrogen fuel cell are sent to the hydrogen fuel heat utilization device for combustion. Heat is generated and heat is transferred to the dehydrogenation reactor.
  • the combustion heat utilization rate is higher than 65%, which reduces the use of fuel cell stacks by more than 10%.
  • the heat energy generated by the hydrogen fuel heat utilization device 120 is supplied to the reaction vessel 104 through a heat conduction device (heat conduction oil heat conduction), and the liquid hydrogen source material is in the dehydrogenation reactor in the catalyst. Reacting at a certain temperature to form a liquid hydrogen storage carrier and hydrogen, and a part of the generated hydrogen is sent to the hydrogen fuel cell 106 through the pipeline. Converted into electrical energy, another part of the hydrogen and hydrogen fuel cell purge exhaust gas is sent to the hydrogen fuel heat utilization device for combustion to generate heat, and the heat is supplied to the dehydrogenation reactor via the heat transfer device (the medium is a heat transfer oil).
  • the combustion heat utilization rate is higher than 60%, and the use of fuel cell stacks is reduced by more than 10%.
  • Fig. 13 is a schematic view showing the structure of the dehydrogenation heat utilization device.
  • the separator between the hydrogen fuel heat utilization device and the dehydrogenation reaction vessel is partitioned, and the heat energy generated by the hydrogen fuel heat utilization device is supplied to the dehydrogenation reactor through the heat conduction of the heat pipe.
  • the liquid hydrogen source material is reacted in a dehydrogenation reactor at a certain temperature to form a liquid hydrogen storage carrier and hydrogen, and a part of the generated hydrogen is transported to a hydrogen fuel cell through a pipeline to be converted into electric energy, and another part of hydrogen and a hydrogen fuel cell.
  • the purge exhaust gas is sent to the hydrogen fuel heat utilization device for combustion to generate heat, and the heat is supplied to the dehydrogenation reactor through the heat conduction device (heat pipe heat conduction).
  • the combustion heat utilization rate is higher than 55%, and the use of fuel cell stacks is reduced by more than 10%.
  • reaction units are separated by a mesh between the sequential connections.
  • the reactor is provided with a temperature controller for controlling the temperature of each heating device.

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Abstract

一种液态氢源材料的脱氢反应系统，包括：用于储存液态氢源材料和液态储氢载体的储存设备（101）；用于将液态氢源材料脱氢的反应釜（104）；用于将液态氢源材料脱氢后的产物氢气和液态储氢载体进行分离的气液分离器（113）。用于储存氢气的缓冲罐（105）；用于加热反应釜的加热装置（107）；通过泵（102）将液态氢源材料经输入管输入所述反应釜（104），在反应釜（104）内进行液态氢源材料的脱氢反应，产生的氢气被输送到缓冲罐（105），同时将脱氢后产生的液态储氢载体输送回储存设备（101）。该常温常压液态氢源材料的脱氢系统用于将液态氢源材料进行脱氢反应，产生的氢气供应燃料电池或内燃机，以转化为电能或机械能以应用于汽车、备用电源、规模化储能、智慧电网、化工、制药等各种工业及民用领域。

Description

一种液态氢源材料的脱氢反应系统 技术领域
本发明涉及有机液态储氢技术领域，特别涉及一种常温常压液态氢源材料的脱氢系统。
背景技术
发展新能源以替代或部分替代不可再生的化石燃料是本世纪人类面临的最大挑战之一。在国务院去年颁布的《“十二五”国家战略性新兴产业发展规划》中，以氢能燃料电池为代表的新能源和新能源汽车作为重点发展产业方向被分别单独列出，并提出了明确的发展目标和发展路线。氢能由于原料来源广泛、无污染且能量转换效率高，是解决未来清洁能源需求问题的首选新能源技术。
氢能技术包括氢的规模制备、储存和运输、高效率使用以及配套基础设施的建设等环节，其中储存和运输,是安全有效的利用氢能是最关键技术之一。目前，工业上主要采用在-253℃的液化氢或350～700个大气压下高压氢等储运技术，高压氢或液化氢技术及其应用所需能耗是制氢成本的20倍以上，且存在泄漏或储氢罐压力过高等安全隐患。如果能够将氢分子吸附在某种载体上，实现常温常压下的安全储存，待使用时，能将氢在温和条件下，可控的释放，则可有效地，安全使用氢能。因此，全球主要的工业国家都在研发基于常温常压的液态有机储氢技术。以德国为例，开发的液态有机储氢技术能够实现较温和条件下的吸/放氢循环，但储氢载体熔点高在常温下是固态重要缺陷；日本目前正在研发基于甲苯等传统有机材料的储氢技术，但脱氢温度过高(大于300℃)，且同样存在副产物毒化燃料电池的问题。因而这两种储氢技术规模化应用受到制约。
中国地质大学(武汉)可持续能源实验室研究团队，在中组部第二批“千人计划”程寒松教授的带领下，在原美国工作基础上，通过长期的探索和研究，发现了一类液态有机共轭分子储氢材料，此类材料具有熔点低(目前开发的技术已低至-20℃)、闪点高(150℃以上)、并在自制高效催化剂作用下，释放气体纯度高(99.99％)、脱氢温度低(约150℃)等特点，且循环寿命高(2000次以上)、可逆性强，并且不产生一氧化碳等毒害燃料电池的气体。作为氢的载体，这类材料在使用过程中始终以液态方式存在，可以像石油一样在常温常压下储存和运输，完全可利用现有汽油输送方式和加油站构架。
发明内容
本发明的目的是提供一种常温常压液态氢源材料的脱氢系统。
为了实现上述目的，本发明采用以下技术方案：一种液态氢源材料的脱氢反应系统，其特征在于包括：
用于储存液态氢源材料和液态储氢载体的储存设备；
用于将液态氢源材料脱氢的反应釜；
用于将液态氢源材料脱氢后的产物氢气和液态储氢载体进行分离的气液分离器。
用于储存氢气的缓冲罐；
用于加热反应釜的加热装置；
所述液态储氢载体包括至少两种不同的储氢组分，储氢组分为不饱和芳香烃或杂环不饱和化合物，且至少一种储氢组分为低熔点化合物，低熔点化合物的熔点低于80℃；
所述储存设备设置有分别存放液态氢源材料和液态储氢载体的储存空间；反应釜为板式、列管式、插片式、塔式或者其他形式；
通过泵将液态氢源材料经输入管输入所述反应釜，在反应釜内进行液态氢源材料的脱氢反应，产生的氢气被输送到缓冲罐，同时将脱氢后产生的液态储氢载体输送回储存设备。
所述反应釜的加热装置为废热交换器、电加热装置、电磁加热装置、化学反应供热装置或微波加热装置，所述输入管外部设置有预热装置，所述储存设备内的液态氢源材料通过预热直接进入反应釜进行脱氢反应。
所述反应釜为薄层板式反应釜或薄层列管式反应釜，所述反应釜插于支架中。
所述支架为多层结构，设置有总进液管、总出液管和总出气管，每层分别设置有分进液管、分出液管、分出气管、加热装置和反应釜卡口；所述反应釜设置有进液口、出液口和出气口；当反应釜插入支架的反应釜卡口时，反应釜进出口、氢气出口分别与支架的总进液管、总出液管和总出气管导通。
所述分进液管、分出液管、分出气管的关口设置有连通阀门，反应釜的进液口、出液口、出气口分别通过连通阀门连接分进液管、分出液管、分出气管。
所述反应釜加热装置为废热交换器、电加热装置、微波加热装置、电磁加热装置或化学反应供热装置。
所述反应釜包括保温层和一个或一个以上反应单元，所述保温层包裹在所有反应单元的外部；所述反应单元包括反应段和加热段，所述反应段的内部填充有催化剂，加热段内设置有加热装置；所述反应单元之间依次连接，反应原料由反应釜的入口进入，依次通过每个反应单元进行吸热反应，反应产物从反应釜的出口排出；所述反应釜内设置有支撑架，反应单元固定在支撑架上，所述反应单元之间以及反应段和加热段之间通过隔层隔开；所述隔 层为网状物、隔膜或分子筛。
所述脱氢反应系统还设置有第一压力传感器，用于检测反应釜压力；
第二压力传感器，用于检测缓冲罐压力；
液位计，用于检测气液分离器内液面位置；
设置在缓冲罐和氢利用装置之间的稳压阀和第二阀门；
控制器，用于采集所述第一、第二压力传感器以及液位计的信号并在满足根据预先设定条件时发送控制信号，所述控制信号用于控制反应设备中原料和反应产物的流量以及脱氢反应的启停。
所述控制器控制反应设备中原料和反应产物的流量以及脱氢反应的启停是通过控制设置在储存设备出口的输入泵、设置在气液分离器气体出口的氢气增压泵、设置在气液分离器液体出口的第一阀门、加热装置的启停，具体为：在正常运行时，第二压力传感器检测到缓冲罐的压力低于第一设定值时，控制器控制输入泵，提高液态氢源材料输送到反应釜的流量，液态氢源材料在反应釜里进行脱氢反应，提高氢气产生速度以提高缓冲罐压力；同时第一压力传感器检测到反应釜的压力高于设定值时，控制器控制启动氢气增压泵，使反应器内部压力低于设定压力；第二压力传感器检测缓冲罐内的压力高于第二设定值时，控制器控制关闭输入泵和反应釜外部的加热装置使反应釜停止工作；液位计检测到气液分离器内液面位置高于设定值时，控制器控制打开第一阀门，让气液分离器内的液态氢源材料流入储存设备。
所述缓冲罐连接氢燃料电池。
所述反应釜与加热装置之间设置有导热装置，所述导热装置通过管道连接氢燃料电池外部设置的管道传热设备，所述导热设备和管道传热设备流动的导热介质为储存液体氢源材料。
所述储存设备连接管道传热设备，导热装置通过输入管连接反应釜，液态氢源材料先进入氢燃料电池外部设置的管道传热设备，将氢燃料电池产生的热量通过导热装置传导给反应釜后，再进入反应釜进行脱氢反应。
所述用于加热反应釜的加热装置为电加热器、电磁加热器或微波加热器。
所述脱氢反应系统还包括蓄电池，用于储存氢燃料电池产生的电能，并供应输入泵、预热装置、反应釜系统设备消耗以及输出。
所述加热装置为氢燃料热利用装置，氢燃料热利用装置连接反应釜，反应釜产生的部分氢气以及氢燃料电池的吹扫尾气在氢燃料热利用装置转为热能提供给反应釜。
所述氢燃料热利用装置将氢气燃烧产生的热能经导热介质通过设置在反应釜外部或 内部的换热管传递给脱氢反应釜，所述导热介质为导热油或金属盐浴；或者所述反应釜和氢燃料热利用装置为一个整体装置，所述氢燃料热利用装置通过将氢气燃烧后产生热能传递给脱氢反应釜。
所述缓冲罐连接氢内燃机。
所述脱氢反应系统还设置有用于储存氧气的储氧罐，氢气和氧气被同时输送入氢内燃机。
所述氢内燃机外部设置有散热器，通过管道与反应釜外部加热装置连接，通过在散热器和加热装置里流动的导热介质传递热量。
所述储存设备连接散热器，加热装置通过输入管连接反应釜，所述导热介质为液态氢源材料。
本发明所提供的常温常压液态氢源材料的脱氢系统可以根据使用领域的不同，对系统内的设备在大小和形式上进行选择，例如对于液态氢源材料和脱氢后液态储氢载体材料的储存装置可以是分开的单独装置单元，也可以是以活动隔板隔开的同一个容器，都能实现本发明的目的。但是，如果用在机动车系统中，从节约机动车空间的角度，优选后者，为同一储罐，中间以可移动或固定的隔板隔开。对于反应釜也可以根据需要采用板式、列管式或塔式，如果用在机动车上，从节约机动车空间的角度，脱氢反应装置为插片式，更节约空间。可根据机动车动力的需要，插片的数量可以定制调整。由于氢内燃机在工作时可以产生高达400℃的温度，氢燃料电池在工作时也能产生50～100℃的温度，而液态氢源材料进行脱氢反应需要120～250℃。液态氢源材料具有在300℃温度保持性能稳定的特定，因此将液态氢源材料作为导热介质来冷却氢内燃机或氢燃料电池，同时将热量传递给脱氢反应釜，传递热量后的液态氢源材料继续进入反应釜进行脱氢化学反应。
本发明所提供的常温常压液态氢源材料的脱氢系统用于将液态储氢材料进行脱氢反应，产生的氢气供应燃料电池或内燃机，以转化为电能或机械能以应用于汽车、电源、储能、化工、制药、移动等各种工业及民用领域。
附图说明
图1是本发明实施例1脱氢反应系统的结构示意图。
图2是本发明实施例2脱氢反应系统的结构示意图。
图3是本发明实施例4脱氢反应系统的结构示意图。
图4是本发明实施例5脱氢反应系统的结构示意图。
图5是本发明实施例6脱氢反应系统的结构示意图。
图6是本发明实施例7脱氢反应系统的结构示意图。
图7是本发明实施例8反应釜、支架和加热装置的结构示意图。
图8是本发明实施例9脱氢反应系统的结构示意图。
图9是本发明实施例10脱氢反应系统的结构示意图。
图10是本发明实施例11脱氢反应系统的结构示意图。
图11是本发明实施例11中反应釜和氢燃料热利用装置为一个整体装置示意图。
图12是实施例12脱氢反应系统的结构示意图。
图13是实施例13中脱氢热利用设备的结构示意图。
图14是实施例14中塔式反应釜示意图。
具体实施方式
下面结合具体的附图和实施例对本发明作进一步的说明。
液态储氢载体是一种可在常温常压下呈现液态的储氢体系，包括至少两种不同的储氢组分，储氢组分为不饱和芳香烃或杂环不饱和化合物，且至少一种储氢组分为低熔点化合物，低熔点化合物的熔点低于80℃。
进一步地，储氢组分选自杂环不饱和化合物，杂环不饱和化合物中的杂原子为N、S、O及P中的一种或多种。
进一步地，杂环不饱和化合物中杂环和芳环的总数为1～20，杂原子的总数为1～20。
进一步地，相对于液态储氢体系的总质量而言，低熔点化合物的质量分数为5～95％。
进一步地，液态储氢体系还包括加氢添加剂，加氢添加剂为极性溶剂和/或非极性溶剂。
进一步地，相对于每克储氢组分而言，加氢添加剂的加入量为0.1～10mL。
进一步地，不同的储氢组分分别选自苯、甲苯、乙苯、邻二甲苯、对二甲苯、苯乙烯、苯乙炔、蒽、萘、芴、苯胺、咔唑、N-甲基咔唑、N-乙基咔唑、N-正丙基咔唑、N-异丙基咔唑、N-正丁基咔唑、吲哚、N-甲基吲哚、N-乙基吲哚、N-丙基吲哚、喹啉、异喹啉、吡啶、吡咯、呋喃、苯并呋喃、噻吩、嘧啶及咪唑所组成的组及其衍生物。
进一步地，极性溶剂选自乙醇、甲醇、乙醚、甲醚、乙腈、乙酸乙酯、甲酰胺、异丙醇、正丁醇、二氧六环、正丁醚、异丙醚、二氯甲烷、氯仿及二氯乙烷中的一种或多种。
进一步地，非极性溶剂选自正己烷、正戊烷、环己烷、均三甲苯、二硫化碳、石油醚及四氯化碳中的一种或多种。
进一步地，储氢体系还包括脱氢添加剂，脱氢添加剂选自十氢化萘、均三甲苯、石 油醚及苯醚中的一种或多种。
进一步地，相对于每克储氢组分而言，脱氢添加剂的加入量为0.1～10mL。
液态储氢载体在加氢催化剂的作用下进行加氢化学反应生成液态氢源材料，液态氢源材料在脱氢催化剂的作用下进行脱氢化学反应还原为液态储氢载体。
用于储存液态氢源材料和液态储氢载体的储存设备，储存设备可以是储存罐或者其他形式，体积可以是微型或车载或大型储存罐体。储存设备可以设置有分别存放液态氢源材料和液态储氢载体的空间：第一存放室和第二存放室，第一和第二存放室各设置有输入口和输出口。第一存放室的输出口设置有输入泵，通过输入泵的运转，液态氢源材料被输入反应釜。储存设备也可以采用分别储存液态氢源材料和液态储氢载体的储存罐，每个储存罐分别设置有有输入口和输出口。
连接泵和反应釜的输入管外部可以设置有预热装置，预热装置可以采用电加热或其他形式，将输入反应釜的液态氢源材料预热至150℃。
反应釜可以采用板式、列管式、塔式或其他形式，内部填充有脱氢催化剂。在反应釜设置有用于加热反应釜的加热装置，加热装置可以采用废热交换器、微波加热装置、电加热装置、热利用装置或其他加热装置，热利用装置是使用氢气、天然气、液化气、汽油或柴油等燃料进行燃烧后产生的热量来进行加热的设备。使得液态氢源材料能在120～250℃温度下进行脱氢反应。
脱氢过程是通过泵将储存在储存设备中的液态氢源材料输入反应釜，120～250℃，0～1MPa大气压下在脱氢催化剂的作用下液态氢源材料反应放出氢气并产生液态储氢载体，氢气被送入缓冲罐，液态储氢载体被送回储存设备。
在板式反应釜或列管式反应釜中，反应釜还可以采用薄层板式反应釜或薄层列管式反应釜，反应釜插于支架中。支架为多层结构，设置有总进液管、总出液管和总出气管，每层分别设置有分进液管、分出液管、分出气管、加热装置和反应釜卡口。反应釜设置有进液口、出液口和出气口；当反应釜插入支架的反应釜卡口时，反应釜进出口、氢气出口分别与支架的总进液管、总出液管和总出气管导通。分进液管、分出液管、分出气管的关口设置有连通阀门，反应釜的进液口、出液口、出气口分别通过连通阀门连接分进液管、分出液管、分出气管。此时反应釜加热装置可以采用废热交换器、电加热装置、微波加热装置、电磁加热装置或化学反应供热装置等各种加热设备。板式反应釜为薄层结构，为保证催化反应效率，反应釜厚度不能厚以避免存在梯度导致反应不稳定，效率不高。反应釜可以根据需要插入支架中，支架为多层结构，可以插入单个或者多个反应釜。支架每层分进液管、分出液管和分 出气管的连通阀门在连接反应釜的进液口、出液口和出气口时为连通状态，否则闭合。加热装置设置在反应釜的前端，或者加热装置的数量超过一个，加热装置之间相隔均匀的距离设置在反应釜外部，加热装置对反应釜进行分段加热。
由于脱氢反应为吸热反应，需要反应釜保持120～250℃的温度才能维持液体氢源材料进行脱氢反应，因此在支架上设置有加热装置，加热装置设置在反应釜的整个外部或者位于反应釜的前端。由于液态氢源材料的脱氢反应在分段加热条件下效率最高，因此优选加热装置的数量超过一个，加热装置之间相隔均匀的距离设置在反应釜外部，加热装置对反应釜进行分段加热。
在塔式反应釜中还可以采用模块化设计，反应釜包括保温层和一个或一个以上反应单元，保温层包裹在所有反应单元的外部。反应单元包括反应段和加热段，反应段的内部填充有催化剂，加热段内设置有加热装置。反应单元之间依次连接，反应原料由反应釜的入口进入，依次通过每个反应单元进行吸热反应，反应产物从反应釜的出口排出。反应釜内设置有支撑架，反应单元固定在支撑架上，反应单元之间以及反应段和加热段之间通过隔层隔开。隔层为网状物、隔膜或分子筛。此时加热装置为电加热器、红外加热器、电磁加热器、微波加热器或者管道加热器。反应釜可以设置有温度控制器，用于控制每个加热装置的温度。催化剂为颗粒状，填充方式为固定床、流化床等。保温层包括保温层内层、保温层外层及内外层之间填充的保温材料，保温层内层和保温层外层之间抽真空，保温层内层涂敷热辐射反射涂层或缠绕热辐射反射材料。
反应物先通过加热段被加热到适合的温度，再在催化剂的作用下进行反应，可以根据反应的实际需要选择反应单元的数量以及保温方式及加热方式，并对加热设备分别进行控制，根据需要分别控制每个加热层的实际补热温度以及热量，根据实际情况添加换热器，极大的提高的能源的利用率，并且使反应更加完全、可控，并可以避免加热过程中因局部过热而产生的副反应。将反应完以后带有热量的气液与入口的原料进行换热，能有效的提高能源利用率。
液态氢源材料在反应釜中被催化分解为氢气和液态储氢载体，反应产物先被输入气液分离装置里进行分离，产生的氢气输送到缓冲罐，液态储氢载体被输送回存放液态储氢载体的空间。
可以对液态氢源材料在脱氢过程中进行控制，以获得稳定的氢气量。可以在脱氢系统中设置：第一压力传感器，用于检测反应釜压力；第二压力传感器，用于检测缓冲罐压力；液位计，用于检测气液分离器内液面位置；控制器，用于采集所述第一、第二压力传感器以 及液位计的信号并在满足根据预先设定条件时发送控制信号，控制信号用于控制反应设备中原料和反应产物的流量以及脱氢反应的启停。储料箱和反应釜之间设置有对液态氢源材料进行预热的预热器。还包括设置在缓冲罐和氢利用装置之间的稳压阀和第二阀门。控制器为PLC、单片机或DCS。
储存设备通过输入泵连接预热器，预热器连接反应釜，反应釜连接气液分离器，气液分离器的出气口连接缓冲罐，出液口连接储料罐，缓冲罐和氢燃料电池相连。反应釜设置有加热装置，整个系统使用PLC控制。
在反应釜中设置有第一压力传感器，用于检测反应釜压力。在缓冲罐中设置有第二压力传感器，用于检测缓冲罐压力。在气液分离器中设置由液位计，用于检测气液分离器内液面位置。第一、第二压力传感器以及液位计的信号发送给PLC，在满足预先设定条件时发送控制信号控制设置在储料箱和预热器管线上的输入泵、设置在气液分离器气体出口的氢气增压泵、设置在气液分离器液体出口的第一阀门、加热装置的启停。在缓冲罐和氢利用装置之间的稳压阀和第二阀门。
在正常运行时，第二压力传感器检测到缓冲罐的压力低于第一设定值时，PLC控制输入泵，提高液态氢源材料输送到预热器的流量，液态氢源材料被预热后被输送到填充有脱氢催化剂的反应釜，液态氢源材料在反应釜里进行脱氢反应，提高氢气产生速度以提高缓冲罐压力。氢气通过稳压阀和第二阀门被输入氢燃料电池。
同时第一压力传感器检测到反应釜的压力高于设定值时，PLC控制启动氢气增压泵，使反应器内部压力低于设定压力。
第二压力传感器检测缓冲罐内的压力高于第二设定值时，PLC控制关闭输入泵和反应釜外部的加热装置使反应釜停止工作。
液位计检测到气液分离器内液面位置高于设定值时，PLC控制打开第一阀门，让气液分离器内的液态储氢载体流入储料箱。
液态氢源材料和液态储氢载体被储存在储料罐中，储料罐设置有分别存放液态氢源材料和液态储氢载体的空间：第一存放室和第二存放室，两个存放室之间隔以活动隔板。
打开第二阀门，缓冲罐内储存的氢气被输入氢燃料电池进行启动，正常运行时当缓冲罐的第二压力传感器检测到罐内的压力低于第一设定值时，通过PLC增大输入泵输入液态氢源材料的流量，液态氢源材料通过输送泵被输送入预热器，预热到100～250℃后进入反应釜，在120～250℃、脱氢催化剂的作用下进行脱氢化学反应，反应产物进入气液分离器。
在反应釜的第一压力传感器检测到反应釜内的压力高于设定值时，通过PLC控制启动氢气增压泵，气液分离器中的氢气通过氢气增压泵储存在缓冲罐中，缓冲罐内的压力为0.03～1MPa，保持反应釜中的压力为常压或微负压。氢气通过稳压阀以0.03～0.06MPa压力被输送到氢燃料电池。
气液分离器中的液态储氢载体达到设定的液位，通过PLC控制第一阀门的开度来输送回储料箱的第二存放室中。
当缓冲罐的第二压力传感器检测到罐内的压力低于第一设定值时，通过PLC控制增大输入泵的流量，增大进行脱氢反应的液态氢源材料的流量。
在缓冲罐的第二压力传感器检测到罐内的压力高于第二设定值时，通过PLC控制关闭输入泵和反应釜外部的加热装置，停止脱氢反应。
在关闭阀门二氢利用装置停止工作后，脱氢反应会减慢最终停止，该段时间内产生的氢气可以通过氢气增压泵输入缓冲罐内，作为下次启动使用。
氢气从缓冲罐可以被输送至氢燃料电池转化为电能。此时反应釜的加热装置为废热交换器、电加热装置、微波加热装置、电磁加热装置或化学反应供热装置。氢源材料储罐和反应釜之间也可以设置有预热装置。所述储罐内的液态氢源材料通过预热后直接进入反应釜进行脱氢反应。
或者在反应釜与加热装置之间设置有导热装置，导热装置通过管道连接氢燃料电池外部设置的管道传热设备，导热设备和管道传热设备流动的导热介质为储存液态氢源材料。
液态氢源材料先进入氢燃料电池外部设置的管道传热设备，将氢燃料电池产生的热量通过导热装置传导给反应釜后，再进入反应釜进行脱氢反应。
氢燃料电池在工作时能产生50～100℃的温度，而液态氢源材料进行脱氢反应需要120～250℃。可以充分利用氢燃料电池所产生的热能。
在氢能转化为电能时，还可以设置有蓄电池，用于储存氢燃料电池产生的电能，并供应泵、加热装置等系统设备消耗以及输出。储存设备储存的液态氢源材料通过输入泵输送到预热装置进行加热，再进入反应釜中，在一定温度、催化剂的条件下产生氢气和液态储氢载体，产物在气液分离器中分离后，液态储氢载体被输送回储存设备，氢气进入缓冲罐，脱氢反应能产生一定的压力，缓冲罐与脱氢反应釜相连也具有一定的压力，氢气进入氢燃料电池转化为电能，产生的电能部分用于供应泵、加热装置等系统设备消耗，其余输出；在使用过程中部分电能会储存在蓄电池中，可供下次启动使用。
由于氢燃料电池吹扫尾气的主要成分为氢气，而脱氢系统中的脱氢反应釜工作时需 要热量，如果将供氢系统产生的氢气通过燃料电池发电并通过电转换为热的装置供给脱氢系统，在相同净输出功率的情况下，使用的燃料电池额定功率会变大，并且氢气燃烧的热利用率较高。因此为反应釜加热的加热装置可以为氢燃料热利用装置，氢燃料热利用装置连接反应釜，反应釜产生的部分氢气以及氢燃料电池的吹扫尾气在氢燃料热利用装置转为热能提供给反应釜。氢燃料热利用装置将氢气燃烧产生的热能经导热介质通过设置在反应釜外部或内部的换热管传递给脱氢反应釜，导热介质为导热油或金属盐浴；或者脱氢热利用设备中的脱氢反应釜和氢燃料热利用装置为一个整体装置，氢燃料热利用装置通过将氢气燃烧后产生热能传递给脱氢反应釜，这样可以提高能量利用率。
氢气从缓冲罐可以被输送至氢内燃机转化为机械能。由于液态氢源材料单位体积可以提供的氢气量高于高压储氢技术和固体储氢技术，因此可以大大减小储存液态氢源材料的空间，因而可在汽车、火车、船等领域应用时，可以留有足够的空间加装氧气罐。在现有技术使用氢内燃机的氢能源汽车上，由于没有足够的空间加装氧气罐，氢内燃机内部氢气直接和空气中的氧气进行反应，空气中的氮气，在高温下和氧气反应产生氮氧化合物，氮氧化合物是致癌物质。尤其是在高原地区，空气中的含氧量较低，较易产生氮氧化合物。而本发明采用直接氧气进入氢内燃机进行反应，不会产生氮氧化合物，不需要加装尾气处理装置，大大节省了成本，更加节能环保。
此外，内燃机工作过程中有很多能量以热量的形式释放，工作温度可达400℃以上，目前的汽油、柴油内和燃气内燃机都是通过冷却系统将热量带走，然后散热浪费掉。而由于脱氢反应是一个吸热过程，反应温度在120～250℃，而内燃机释放的热量可以通过换热系统，特别是用氢源材料本身做为冷凝剂，加以利用，整个过程起到了冷却和提高能源利用率的效果。氢内燃机外部设置有散热器，通过管道与反应釜外部加热装置连接。使用氢源材料本身做为冷凝剂时，储存设备连接散热器，加热装置通过输入管连接反应釜，导热介质为液态氢源材料。
实施例1
如图1所示，储存设备为储存罐，液态氢源材料和液态储氢载体分别存放在不同的储存罐101内，每个储存罐分别设置有有输入口和输出口，在存放液态氢源材料储存罐的输出口设置有泵102，连接泵和反应釜的输入管外部设置有预热装置103，预热装置为电加热装置。通过泵的运转，液态氢源材料被输入反应釜104。反应釜为塔式反应釜，内部填充有脱氢催化剂。液态氢源材料在反应釜中被分解为氢气和液态储氢载体，储氢载体被输送回存放储氢载体的空间。氢气被输送到缓冲罐105，然后从缓冲罐输送至氢燃料电池106。在反应釜外 部设置有电加热装置107将反应釜的温度保持在120～250℃。
实施例2
如图2所示，储存设备为车载储存罐，储存罐设置有分别存放液态氢源材料液态和储氢载体的空间：第一存放室108和第二存放室109，第一和第二存放室各设置有输入口和输出口。第一存放室的输出口设置有泵102，连接泵和反应釜的输入管外部设置有预热装置103，预热装置为由电瓶供电的电加热装置。通过泵的运转，液态氢源材料被输入反应釜104。反应釜为板式反应釜，内部填充有脱氢催化剂。液态氢源材料在反应釜中被分解为氢气和液态储氢载体，，液态储氢载体被输送回存放液态储氢载体的第二存放室。氢气被输送到缓冲罐105，然后从缓冲罐输送至氢内燃机110。在反应釜外部设置有微波加热装置111将反应釜的温度保持在120～250℃。
实施例3
储存设备为微型储存罐，储存罐设置有分别存放液态氢源材料和储氢载体的空间：第一存放室和第二存放室，第一和第二存放室各设置有输入口和输出口。第一存放室的输出口设置有泵。
通过泵将液态氢源材料输入氢内燃机外部设置的管道传热设备，将氢内燃机产生的热量通过加热装置传导给反应釜后，再进入反应釜进行脱氢反应，反应釜为列管式反应釜，内部填充有脱氢催化剂。液态氢源材料在反应釜中被分解为氢气和储氢载体，储氢载体被输送回存放储氢载体的空间。氢气被输送到缓冲罐，然后从缓冲罐输送至氢内燃机。在反应釜外部设置有电加热装置使反应釜的温度保持在120～250℃。
实施例4
从图3可以看出，脱氢反应系统，包括：用于储存液态氢源材料和液态储氢载体的储罐、用于将液态氢源材料脱氢的反应釜104、用于储存氢气的缓冲罐105、用于给反应釜加热的电加热装置107和氢燃料电池106。
用于储存液态氢源材料和液态储氢载体的储罐设置有分别存放液态氢源材料和液态储氢载体的空间：第一存放室108和第二存放室109，两个存放室之间隔以活动隔板112。第一和第二存放室各设置有输入口和输出口，第一存放室的输出口设置有泵102，通过泵的运转，液态氢源材料经输入管被输入反应釜。反应釜可以是板式反应釜，内部填充有脱氢催化剂。板式反应釜可以是插片式的，并可以根据汽车排量的需求，相应增加插片数量。
连接泵和反应釜的输入管外部设置有预热装置103，其目的在于提高具体应用过程中，脱氢反应的效率和速度。预热装置可以采用电加热或其他形式，将输入反应釜的液态氢源材 料预热至150℃。
液态氢源材料在反应釜中被分解为氢气和液态储氢载体，液态储氢载体被输送回储氢罐存放液态储氢载体的第二存放室。由于两个存放室之间隔以活动隔板，在当液态氢源材料被输出后，第一存放室的空间减小，而第二存放室的空间增大，可以用于存放输送回来的液态储氢载体，有利于节省空间。在液态氢源材料被脱氢生成液态储氢载体后，可以通过第二存放室的输出口抽出液态储氢载体，同时向第一存放室的输入口灌入液态氢源材料。
反应釜产生的氢气被输送到缓冲罐，然后进入氢燃料电池。反应釜需要120～250℃的温度才能维持液态氢源材料进行脱氢反应，因此在反应釜外部设置有加热装置，加热装置为电加热器。
储氢设备通过泵将液态氢源材料经输入管输入反应釜，反应釜将液态氢源材料脱氢后产生的氢气输送到缓冲罐，同时将脱氢后产生的液态储氢载体输送回储氢罐，缓冲罐内的氢气被送进入氢燃料电池，化学能转化为电能，电能转为动能带动发动机的运转。
实施例5
由图4可以看出，脱氢反应系统包括：用于储存液态氢源材料和液态储氢载体的储罐、用于将液态氢源材料脱氢的反应釜104、用于储存氢气的缓冲罐105、气液分离装置113，微波加热装置111、导热装置114和氢燃料电池106。
用于储存液态氢源材料和液态储氢载体的储罐设置有分别存放液态氢源材料和液态储氢载体的空间：第一存放室108和第二存放室109，两个存放室之间隔以活动隔板112。第一和第二存放室各设置有输入口和输出口，第一存放室的输出口设置有泵102，通过泵的运转，液态氢源材料经输入管被输出。反应釜与加热装置之间设置有导热装置，导热装置通过管道连接氢燃料电池外部设置的管道传热设备115，加热设备和管道传热设备流动的导热介质为储存液体氢源材料。
通过泵将液态氢源材料输入氢燃料电池外部设置的管道传热设备，将氢燃料电池产生的热量通过加热装置传导给反应釜后，再进入反应釜进行脱氢反应，反应釜为列管式反应釜，内部填充有脱氢催化剂。液态氢源材料在反应釜中被催化分解，产物被送入气液分离装置里进行分离为氢气和液态储氢载体，液态储氢载体被输送回存放储氢载体的空间。氢气被输送到缓冲罐，然后从缓冲罐输送至氢燃料电池。但由于氢燃料电池的放热在50～100℃，不足以维持反应釜的反应，因此在反应釜外部设置有微波加热装置使反应釜的温度保持在120～250℃。
实施例6
从图5可以看出，用于储存液态氢源材料和液态储氢载体的储氢罐设置有分别存放液态氢源材料和液态储氢载体的空间：第一存放室108和第二存放室109，两个存放室之间隔以活动隔板112。第一和第二存放室各设置有输入口和输出口，第一存放室的输出口设置有泵102，通过泵的运转，液态氢源材料经输入管被输入反应釜104。反应釜采用板式反应釜，内部填充有脱氢催化剂。
连接泵和反应釜的输入管外部设置有预热装置103，预热装置采用电加热器，将输入反应釜的液态氢源材料预热至150℃。
液态氢源材料在反应釜中被催化分解，液态储氢载体被输送回储氢罐存放液态储氢载体的第二存放室。由于两个存放室之间隔以活动隔板，在当液态氢源材料被输出后，第一存放室的空间减小，而第二存放室的空间增大，可以用于存放输送回来的液态储氢载体，有利于节省空间。在液态氢源材料被脱氢生成液态储氢载体后，可以通过第二存放室的输出口抽出液态储氢载体，同时向第一存放室的输入口灌入液态氢源材料。
反应釜中产生的氢气被输送到缓冲罐105，然后进入氢内燃机110，同时通过泵按1：8质量比向氢内燃机输入氢气和储氧罐116内的氧气，氢气和氧气在氢内燃机内进行化学能到机械能的转化，带动汽车或者或者或者船等交通设备的运转。氢内燃机会产生400℃左右的高温，而反应釜需要120～250℃的温度才能维持液态氢源材料进行脱氢反应，因此在氢内燃机和反应釜外部设置有换热装置：设置在氢内燃机外部的散热器117和设置在反应釜的外部的加热器118。散热器和加热器之间通过管路相连，导热介质冷却氢内燃机并加热反应釜。通过热交换，可以充分利用氢内燃机产生的热能。在管路上设置有泵保证导热介质在散热器和加热器之间的流动。
实施例7
从图6可以看出，用于储存液态氢源材料和液态储氢载体的储氢罐设置有分别存放液态氢源材料和液态储氢载体的空间：第一存放室108和第二存放室109，两个存放室之间隔以活动隔板112。第一和第二存放室各设置有输入口和输出口，第一存放室的输出口设置有泵102，通过泵的运转，液态氢源材料被输入到设置在氢内燃机外部的散热器117的管道内，设置在反应釜的外部的加热器118和散热器之间通过管路相连，液态氢源材料通过热交换冷却氢内燃机并加热反应釜，最后通过输入管进入反应釜104。
反应釜采用列管式反应釜，内部填充有脱氢催化剂。液态氢源材料在反应釜中被催化分解，产物被送入气液分离装置113里进行分离为氢气和液态储氢载体，液态储氢载体被输送回储氢罐存放液态储氢载体的第二存放室。气液分离装置将氢气输送到缓冲罐105，然 后进入氢内燃机110，同时通过泵按1：8质量比向氢内燃机输入氢气和储氧罐116内的氧气，氢气和氧气在氢内燃机内进行化学能到机械能的转化，带动汽车或者或者或者船等交通设备的运转。
将脱氢系统运用在小型汽车上，储氢罐的体积为60～100L，即可提供4.5～5.8kg的氢气，可以小型汽车行驶500公里。
将脱氢系统运用在卡车上，储氢罐的体积为150～250L，即可提供11.3～14.5kg的氢气，可使卡车行驶500公里。
实施例8
如图7所示，为反应釜、支架和加热装置的结构示意图。支架为多层结构，设置有总进液管201、总出液管202和总出气管203，每层分别设置有分进液管204、分出液管205、分出气管206和反应釜卡口207。分进液管、分出液管、分出气管的关口设置有连通阀门208。
反应釜104为薄层列管式反应釜，数量为5个，可以根据需要进行增减。内部填充有脱氢催化剂和惰性材料。反应釜设置有进液口210、出液口211和出气口212，反应釜可插入支架中的加热装置内通过进液口、出液口和出气口分别与分进液管、分出液管和分出气管相连。
加热装置为电加热装置107，每层加热装置的数量为4个，加热装置之间相隔均匀的距离设置在反应釜外部，加热装置对反应釜进行分段加热。
液态氢源材料通过总进液管进入分进液管进入反应釜，反应釜在120～250℃下在脱氢催化剂的作用下将液体氢源材料分解为氢气和液体储氢载体，氢气通过分出气管进入总出气管被送入储气罐，液体储氢载体通过分出液管进入总出液管被倒入储液罐。
实施例9
如图8所示，脱氢反应系统包括：储存设备101、预热器103、泵102、反应釜104、气液分离器113和氢燃料电池106。储存设备用于储存液态氢源材料和液态储氢载体，设置有分别存放液态氢源材料和液态储氢载体的空间，两个空间之间以活动隔板112相连。储存设备储存储存液态氢源材料一端的输液口通过管道连接预热器，管道上设置有泵，预热器连接反应釜，反应釜连接气液分离器，气液分离器的出气口连接氢燃料电池，出液口连接设备储存储存液态储氢载体的进液口。
储存设备储存的液态氢源材料通过泵输送到预热器加热到150℃，再进入反应釜中，在170℃、空速为1、催化剂的条件下产生氢气和液态储氢载体，产物在气液分离器中分离后，液态储氢载体被输送回储存设备，氢气进入缓冲罐105中，压力约1～6bar，然后将氢气 减压至0.3～0.7bar通入氢燃料电池转化为电能，产生电能的25％用于供应泵、预热器、反应釜等系统设备消耗，其余输出；关闭系统时，反应釜仍具有一定的温度，还会继续反应一段时间，期间产生的氢气被储存在缓存罐中供下次启动时使用。
实施例10
如图9所示，脱氢反应系统包括：储存设备101、预热器103、泵102、反应釜104、气液分离器113、氢燃料电池106和蓄电池119。储存设备用于储存液态氢源材料和液态储氢载体，设置有分别存放液态氢源材料和液态储氢载体的空间，两个空间之间以活动隔板相连。储存设备储存储存液态氢源材料一端的输液口通过管道连接预热器，管道上设置有泵，预热器连接反应釜，反应釜连接气液分离器，气液分离器的出气口连接氢燃料电池，出液口连接设备储存储存液态储氢载体的进液口。氢燃料电池连接蓄电池。
储存设备储存的液态氢源材料通过泵输送到预热器加热到160℃，再进入反应釜中，在190℃、空速为2、催化剂的条件下产生氢气和液态储氢载体，产物在气液分离器中分离后，液态储氢载体被输送回储存设备，氢气进入缓冲罐105，压力约1～6bar，然后将氢气减压至0.3～0.7bar通入氢燃料电池转化为电能，产生的电能部分储存在蓄电池中，蓄电池电能的20％用于供应泵、预热器、反应釜等系统设备消耗，其余输出；关闭系统时，反应釜仍具有一定的温度，还会继续反应一段时间，期间产生的氢气通过氢燃料电池产生电能并储存在蓄电池中供下次启动时使用。
实施例11
如图10所示为脱氢反应系统的结构示意图，图11为直接将氢燃料热利用装置与反应釜结合设计成整体的设备结构示意图，由内层至外层分别是燃烧反应区、脱氢反应区和废热利用区，燃烧反应区也就是氢燃料热利用装置，而脱氢反应区也就是脱氢反应釜。
氢气和空气在燃烧反应区进行燃烧并给脱氢反应区内侧供热，生成的尾气经过废热利用区给脱氢反应区外侧供热，在脱氢反应区内氢源材料在一定温度和催化剂的作用下反应生成液态储氢载体和氢气，生成的氢气中一部分通过管路被输送到氢燃料电池转化成电能，另一部分氢气以及氢燃料电池的吹扫尾气被送入氢燃料热利用装置中燃烧产生热量，热量传递给脱氢反应釜。燃烧热利用率高于65％，减少了燃料电池电堆的使用10％以上。
实施例12
如图12所示为脱氢反应系统的结构示意图，氢燃料热利用装置120产生的热能通过导热装置(导热油导热)将热量供给反应釜104，液态氢源材料在脱氢反应釜中在催化剂、一定温度下反应生成液态储氢载体和氢气，生成的氢气中一部分通过管路被输送到氢燃料电池106 转化成电能，另一部分氢气和氢燃料电池的吹扫尾气被送入氢燃料热利用装置中燃烧产生热量，热量经导热装置(介质为导热油)给脱氢反应釜供热。燃烧热利用率高于60％，减少燃料电池电堆的使用10％以上。
实施例13
如图13为脱氢热利用设备的结构示意图，氢燃料热利用装置与脱氢反应釜之间间隔着隔板，氢燃料热利用装置产生的热能通过热管导热将热量供给脱氢反应釜。液态氢源材料在脱氢反应釜中在催化剂、一定温度下反应生成液态储氢载体和氢气，生成的氢气中一部分通过管路被输送到氢燃料电池转化成电能，另一部分氢气以及氢燃料电池的吹扫尾气被送入氢燃料热利用装置中燃烧产生热量，热量经导热装置(热管导热)给脱氢反应釜供热。燃烧热利用率高于55％，减少燃料电池电堆的使用10％以上。
实施例14
图14为塔式反应釜示意图，此反应釜采用模块化设计，，反应釜包括保温层和3个反应单元，保温层包裹在所有反应单元的外部，下部设置有入口,上部设置有出口。保温层包括保温层内层、保温层外层，保温层内层外表面依次间隔包裹2层保温材料和2层反光锡纸，保温层内层和保温层外层之间抽真空形成真空层，并填充岩棉。反应釜内设置有支撑架，反应单元固定在支撑架上。反应单元包括反应段和加热段，反应层的内部填充有催化剂，加热层内设置有电加热器。由于产生的气体带有大量的热量，可以给进入液进行换热。
反应单元之间依次连接之间通过网状物隔开。
反应釜设置有温度控制器，用于控制每个加热装置的温度。
液态氢源材料脱氢温度过低会使脱氢率降低，温度过高容易发生副反应。将3个反应单元温度控制在180℃、190℃、200℃，液态氢源材料为十二氢咔唑，脱氢产物为咔唑,脱氢率达到95％以上，无副反应发生。
虽然本发明已以较佳实施例公开如上，但实施例和附图并不是用来限定本发明，任何熟悉此技艺者，在不脱离本发明之精神和范围内，自当可作各种变化或润饰，但同样在本发明的保护范围之内。因此本发明的保护范围应当以本申请的权利要求保护范围所界定的为准。

Claims (20)

  1. 一种液态氢源材料的脱氢反应系统，其特征在于包括：
    用于储存液态氢源材料和液态储氢载体的储存设备；
    用于将液态氢源材料脱氢的反应釜；
    用于将液态氢源材料脱氢后的产物氢气和液态储氢载体进行分离的气液分离器；
    用于储存氢气的缓冲罐；
    用于加热反应釜的加热装置；
    所述液态储氢载体包括至少两种不同的储氢组分，储氢组分为不饱和芳香烃或杂环不饱和化合物，且至少一种储氢组分为低熔点化合物，低熔点化合物的熔点低于80℃；
    所述储存设备设置有分别存放液态氢源材料和液态储氢载体的储存空间；
    通过泵将液态氢源材料经输入管输入所述反应釜，在反应釜内进行液态氢源材料的脱氢反应，产生的氢气输送到缓冲罐，同时将脱氢后产生的液态储氢载体输送回储存设备。
  2. 根据权利要求1所述的液态氢源材料的脱氢反应系统，其特征在于：所述反应釜的加热装置为废热交换器、电加热装置、电磁加热装置、化学反应供热装置或微波加热装置，所述输入管外部设置有预热装置，所述储存设备内的液态氢源材料通过预热直接进入反应釜进行脱氢反应。
  3. 根据权利要求1所述的液态氢源材料的脱氢反应系统，其特征在于：所述反应釜为薄层板式反应釜或薄层列管式反应釜，所述反应釜插于支架中。
  4. 根据权利要求3所述的液态氢源材料供氢反应系统，其特征在于：所述支架为多层结构，设置有总进液管、总出液管和总出气管，每层分别设置有分进液管、分出液管、分出气管、加热装置和反应釜卡口；所述反应釜设置有进液口、出液口和出气口；当反应釜插入支架的反应釜卡口时，反应釜进出口、氢气出口分别与支架的总进液管、总出液管和总出气管导通。
  5. 根据权利要求4所述的液态氢源材料供氢反应系统，其特征在于：所述分进液管、分出液管、分出气管的关口设置有连通阀门，反应釜的进液口、出液口、出气口分别通过连通阀门连接分进液管、分出液管、分出气管。
  6. 根据权利要求5所述的液态氢源材料供氢反应系统，其特征在于：所述反应釜加热装置为废热交换器、电加热装置、微波加热装置、电磁加热装置或化学反应供热装置。
  7. 根据权利要求1所述的液态氢源材料的脱氢反应系统，其特征在于：所述反应釜包括保温层和一个或一个以上反应单元，所述保温层包裹在所有反应单元的外部；所述反应单元包括反应段和加热段，所述反应段的内部填充有催化剂，加热段内设置有加热装置；所述反应单元之间依次连接，液态氢源材料由反应釜的入口进入，依次通过每个反应单元进行脱氢反 应，反应产物从反应釜的出口排出；所述反应釜内设置有支撑架，反应单元固定在支撑架上，所述反应单元之间以及反应段和加热段之间通过隔层隔开；所述隔层为网状物、隔膜或分子筛。
  8. 根据权利要求1所述的液态氢源材料的脱氢反应系统，其特征在于：所述脱氢反应系统还设置有第一压力传感器，用于检测反应釜压力；
    第二压力传感器，用于检测缓冲罐压力；
    液位计，用于检测气液分离器内液面位置；
    设置在缓冲罐和氢利用装置之间的稳压阀和第二阀门；
    控制器，用于采集所述第一、第二压力传感器以及液位计的信号并在满足根据预先设定条件时发送控制信号，所述控制信号用于控制反应设备中原料和反应产物的流量以及脱氢反应的启停。
  9. 根据权利要求8所述的液态氢源材料的脱氢反应系统，其特征在于：所述控制器控制反应设备中原料和反应产物的流量以及脱氢反应的启停是通过控制设置在储存设备出口的输入泵、设置在气液分离器气体出口的氢气增压泵、设置在气液分离器液体出口的第一阀门、加热装置的启停，具体为：在正常运行时，第二压力传感器检测到缓冲罐的压力低于第一设定值时，控制器控制输入泵，提高液态氢源材料输送到反应釜的流量，液态氢源材料在反应釜里进行脱氢反应，提高氢气产生速度以提高缓冲罐压力；同时第一压力传感器检测到反应釜的压力高于设定值时，控制器控制启动氢气增压泵，使反应器内部压力低于设定压力；第二压力传感器检测缓冲罐内的压力高于第二设定值时，控制器控制关闭输入泵和反应釜外部的加热装置使反应釜停止工作；液位计检测到气液分离器内液面位置高于设定值时，控制器控制打开第一阀门，让气液分离器内的液态氢源材料流入储存设备。
  10. 根据权利要求1所述的液态氢源材料的脱氢反应系统，其特征在于：所述缓冲罐连接氢燃料电池。
  11. 根据权利要求10所述的液态氢源材料的脱氢反应系统，其特征在于：所述反应釜与加热装置之间设置有导热装置，所述导热装置通过管道连接氢燃料电池外部设置的管道传热设备，所述导热设备和管道传热设备流动的导热介质为储存液体氢源材料。
  12. 根据权利要求11所述的液态氢源材料的脱氢反应系统，其特征在于：所述储存设备连接管道传热设备，导热装置通过输入管连接反应釜，液态氢源材料先进入氢燃料电池外部设置的管道传热设备，将氢燃料电池产生的热量通过导热装置传导给反应釜后，再进入反应釜进行脱氢反应。
  13. 根据权利要求12所述的液态氢源材料的脱氢反应系统，其特征在于：所述用于加热反应釜的加热装置为电加热器、电磁加热器或微波加热器。
  14. 根据权利要求10所述的液态氢源材料的脱氢反应系统，其特征在于：所述脱氢反应系统还包括蓄电池，用于储存氢燃料电池产生的电能，并供应输入泵、加热装置等系统设备消耗以及输出。
  15. 根据权利要求10所述的液态氢源材料的脱氢反应系统，其特征在于：所述加热装置为氢燃料热利用装置，氢燃料热利用装置连接反应釜，反应釜产生的部分氢气以及氢燃料电池的吹扫尾气在氢燃料热利用装置转为热能提供给反应釜。
  16. 根据权利要求15所述的液态氢源材料的脱氢反应系统，其特征在于：所述氢燃料热利用装置将氢气燃烧产生的热能经导热介质通过设置在反应釜外部或内部的换热管传递给脱氢反应釜，所述导热介质为液态氢源材料、导热油或金属盐浴；或者所述反应釜和氢燃料热利用装置为一个整体装置，所述氢燃料热利用装置通过将氢气燃烧后产生热能传递给脱氢反应釜。
  17. 根据权利要求1所述的液态氢源材料的脱氢反应系统，其特征在于：所述缓冲罐连接氢内燃机，氢气和氧气被同时输送入氢内燃机。
  18. 根据权利要求17所述的液态氢源材料的脱氢反应系统，其特征在于：所述脱氢反应系统还设置有用于储存氧气的储氧罐。
  19. 根据权利要求18所述的液态氢源材料的脱氢反应系统，其特征在于：所述氢内燃机外部设置有散热器，通过管道与反应釜外部加热装置连接通过在散热器和加热装置里流动的导热介质传递热量。
  20. 根据权利要求19所述的液态氢源材料的脱氢反应系统，其特征在于：所述储存设备连接散热器，加热装置通过输入管连接反应釜，所述导热介质为液态氢源材料。
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JP2021535057A (ja) * 2018-04-17 2021-12-16 エレクトリック−グローバル・エナジー・ソリューションズ・リミテッド 液体水素担体からの水素ガス抽出のためのバッチシステムおよび方法
JP7387711B2 (ja) 2018-04-17 2023-11-28 エレクトリック－グローバル・エナジー・ソリューションズ・リミテッド 液体水素担体からの水素ガス抽出のためのバッチシステムおよび方法
CN113571748A (zh) * 2021-06-04 2021-10-29 华能苏州热电有限责任公司 一种耦合固体氧化物燃料电池的lohc系统
CN113571748B (zh) * 2021-06-04 2023-09-22 华能苏州热电有限责任公司 一种耦合固体氧化物燃料电池的lohc系统
CN113540511A (zh) * 2021-07-16 2021-10-22 西安海望能源科技有限公司 一种高效热量回收的有机液体集成能源系统
CN113540511B (zh) * 2021-07-16 2024-03-01 陕西氢易能源科技有限公司 一种高效热量回收的有机液体集成能源系统
CN117613297A (zh) * 2023-11-29 2024-02-27 江苏兴邦能源科技有限公司 一种氢能两轮车用储氢罐热管理系统
CN117613297B (zh) * 2023-11-29 2024-05-31 江苏兴邦能源科技有限公司 一种氢能两轮车用储氢罐热管理系统

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