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 PDFInfo
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- H—ELECTRICITY
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Description
Claims (20)
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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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WO2019068387A1 (de) * | 2017-10-05 | 2019-04-11 | Hydrogenious Technologies Gmbh | Anlage und verfahren zur bereitstellung und weiteren nutzung von wasserstoffgas |
KR20200066331A (ko) * | 2017-10-05 | 2020-06-09 | 하이드로지니어스 엘오에이치씨 테크놀로지스 게엠베하 | 수소 기체를 제공하고 추가로 이용하기 위한 시스템 및 방법 |
KR102549839B1 (ko) | 2017-10-05 | 2023-06-29 | 하이드로지니어스 엘오에이치씨 테크놀로지스 게엠베하 | 수소 기체를 제공하고 추가로 이용하기 위한 시스템 및 방법 |
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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JP6506468B2 (ja) | 2019-04-24 |
US20180069255A1 (en) | 2018-03-08 |
JP2018514501A (ja) | 2018-06-07 |
EP3281912A4 (en) | 2018-09-05 |
EP3281912A1 (en) | 2018-02-14 |
US10586993B2 (en) | 2020-03-10 |
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