CN110429308B - Methanol hydrogen production power generation system - Google Patents
Methanol hydrogen production power generation system Download PDFInfo
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- CN110429308B CN110429308B CN201910722797.9A CN201910722797A CN110429308B CN 110429308 B CN110429308 B CN 110429308B CN 201910722797 A CN201910722797 A CN 201910722797A CN 110429308 B CN110429308 B CN 110429308B
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- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
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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
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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
- H01M8/22—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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- 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
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
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- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0816—Heating by flames
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- C—CHEMISTRY; METALLURGY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B2203/1258—Pre-treatment of the feed
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
A methanol hydrogen production power generation system comprises a heat exchanger, a methanation reactor, a reforming hydrogen production device and a hydrogen fuel cell; the reforming hydrogen production device comprises a sealed box body, wherein a combustion chamber, a reforming chamber and a purifying chamber are arranged in the sealed box body, and the combustion chamber is used for heating the reforming chamber and the purifying chamber; the reforming chamber comprises a reforming shell, a groove is arranged on the bottom surface of the reforming shell, a coil pipe is embedded in the groove, a reaction tube is arranged in the reforming shell, a catalyst is arranged in the reaction tube, and an electric heating rod is embedded in the reforming shell; generating hydrogen-rich in the methanol water in the reforming chamber, and conveying the hydrogen-rich to a purifying chamber, wherein the purifying chamber is used for purifying the hydrogen-rich; the side surface of the reforming shell is provided with a fire guiding groove, and the purifying chamber is provided with an electric heating plate; the purifying chamber is provided with a pure hydrogen outlet which is communicated with an air inlet of the methanation reactor, an air outlet of the methanation reactor is communicated with a hot fluid inlet of the heat exchanger, and a hot fluid outlet of the heat exchanger is communicated with a hydrogen inlet of the hydrogen fuel cell. The invention can realize quick start.
Description
Technical Field
The invention relates to the technical field of hydrogen production and power generation, in particular to a methanol hydrogen production and power generation system.
Background
Hydrogen energy is a clean secondary energy source. In recent years, with the gradual maturing of the development of hydrogen energy application technology and the continuous increase of the global coping climate change pressure, the development of the hydrogen energy industry is focused on all countries of the world, and the hydrogen fuel cell can efficiently and cleanly convert chemical energy into electric energy directly, is a more advanced conversion technology than a conventional heat engine, and brings a great opportunity for the revolution of energy power due to the rapid development of the fuel cell technology.
Along with the development of technology, requirements on energy and standby batteries are more and more strict, and the clean, noise-free and interference-free energy or standby batteries are urgently needed in various fields such as mobile communication base stations, micro stations, emergency vehicles, airport tractors, logistics vehicles, hospital power supply, data center power supply, military and the like. However, if hydrogen is directly used for power generation, safety technical bottlenecks such as manufacturing, storage and transportation exist, and under the background, a technical route for generating power after hydrogen production by using methanol water is more and more emphasized, so that an industry for generating power after hydrogen production by using methanol water is created.
Existing methanol-water hydrogen production power generation plants generally include heavy dutyThe reforming hydrogen production device and the hydrogen power generation module, and the reforming hydrogen production device needs to undergo high-temperature reforming reaction in the hydrogen production process, so that the reforming reactor is a core component of the methanol-water hydrogen production power generation device. The principle of the hydrogen production process by methanol water is as follows: the methanol water fuel is pressurized and gasified by heat absorption, then enters a reforming chamber to carry out reforming reaction together with a catalyst, so as to obtain hydrogen (hydrogen rich) rich in impurities, and the hydrogen passes through a purifier to generate high-purity hydrogen (H) reaching 99.99 percent 2 ) And the CO content is less than or equal to 1 ppm). The hydrogen is converted into normal temperature through heat exchange, and enters a galvanic pile through decompression to generate electrochemical reaction, so as to generate electric energy. The hydrogen production reaction mechanism is as follows:
CH 3 OH（g）→CO+2H 2 ，Δ=-90.64KJ/mol，
CO+H 2 O（g）→CO 2 +H 2 ，Δ=-41.00KJ/mol。
the hydrogen production reaction is a strong endothermic reaction, and heat needs to be continuously supplied to maintain the reaction. The existing reforming hydrogen production device generally utilizes electric heating to enable the temperature to reach the temperature of reforming reaction, and then utilizes purified split gas to introduce combustion, so that the design has the defects of consuming a large amount of electric energy, being influenced by electric heating incapable of high power (generating electricity under the condition of lack of electricity) and being limited in cost, so that the reforming hydrogen production device is enabled to reach the temperature of reforming reaction by utilizing the electric heating at the conventional temperature, the cold starting time is generally longer than 10 hours, and the hydrogen purifier used in the existing reforming hydrogen production device has the limit of service life of cold starting times, thereby influencing the service life of the whole equipment, and in order to avoid cold starting equipment, the reforming hydrogen production device generally has to be always in a hot standby condition, and a large amount of electric energy is consumed for a long time.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art, and provides a methanol hydrogen production power generation system which has the advantages of quick response, high efficiency, long service life, high stability, low running cost and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a methanol hydrogen production power generation system comprises a heat exchanger, a methanation reactor, a reforming hydrogen production device and a hydrogen fuel cell; the reforming hydrogen production device comprises a sealed box body, wherein a combustion chamber, a reforming chamber and a purifying chamber are arranged in the sealed box body, the combustion chamber, the reforming chamber and the purifying chamber are sequentially arranged in a stacked manner from bottom to top, and the combustion chamber is used for heating the reforming chamber and the purifying chamber; the sealed box body is provided with a methanol water inlet and an air inlet, and the air inlet of the sealed box body is communicated with the combustion chamber through a pipeline to provide air; the reforming chamber comprises a reforming shell made of metal materials, a groove is formed in the bottom surface of the reforming shell, a coil pipe for vaporization is embedded in the groove, a reaction tube is arranged in the reforming shell, a catalyst for reforming reaction is arranged in the reaction tube, an electric heating rod is embedded in the reforming shell, the inlet end of the coil pipe is communicated with a methanol water inlet, and the outlet end of the coil pipe is communicated with the inlet end of the reaction tube; the methanol water is subjected to reforming reaction in the reforming chamber to generate hydrogen-rich gas, the hydrogen-rich gas is conveyed to the purifying chamber from the outlet end of the reaction tube array, and the purifying chamber is used for purifying the hydrogen-rich gas to obtain pure hydrogen; the side surface of the reforming shell is provided with a vertical fire guiding groove, the fire guiding groove is used for conducting the purification chamber and the combustion chamber, the fire guiding groove is used for guiding flame generated by the combustion chamber to the purification chamber so as to heat the purification chamber, and the purification chamber is provided with an electric heating plate; the purifying chamber is provided with a pure hydrogen outlet which is communicated with an air inlet of the methanation reactor, an air outlet of the methanation reactor is communicated with a hot fluid inlet of the heat exchanger, and a hot fluid outlet of the heat exchanger is communicated with a hydrogen inlet of the hydrogen fuel cell.
From the above, the invention utilizes the methanol water to generate the hydrogen-rich by reforming reaction in the reforming chamber, the hydrogen-rich is conveyed to the purifying chamber from the outlet end of the reaction tube array, the purifying chamber purifies the hydrogen-rich to obtain pure hydrogen, the methanation reactor carries out methanation treatment on the pure hydrogen, and CO possibly existing in the pure hydrogen are purified 2 Converting into methane, cooling the pure hydrogen by the heat exchanger, reducing the temperature of the pure hydrogen to normal temperature, and then conveying the pure hydrogen to a hydrogen fuel cell for power generation. In the reforming reaction process, the invention firstly gasifies the methanol water in the coil pipe, and the gasified methanol water steam enters againReaction tube array, reforming reaction under the action of catalyst and generating hydrogen-enriched (H) 2 ,CO,CO 2 ) The hydrogen-enriched gas enters a purifying chamber, and the purifying chamber purifies and separates the hydrogen-enriched gas to obtain high-purity hydrogen gas.
In addition, the reforming chamber adopts the reforming shell made of metal materials, then the methanol water vaporization process and the reforming reaction process are carried out in two stages, the methanol water vaporization process is carried out in the coil pipe, the coil pipe directly heats the coil pipe by utilizing the combustion chamber and the electric heating rod in a mode of being embedded in the groove on the bottom surface of the reforming shell, and the reforming chamber and the purifying chamber are sequentially arranged from bottom to top in a stacked mode, so that the methanol water vaporization heating requirement is efficiently met, the equipment volume and the occupied space can be reduced, and the hydrogen production equipment for the reforming reaction is portable and the application range is enlarged; according to the invention, the combustion chamber is used for heating the reforming chamber and the purifying chamber at the same time, the electric heating plate is started for heating the purifying chamber at the same time, the working temperature of the reforming chamber and the purifying chamber, namely the working temperature of reforming reaction and the purifying working temperature, can be quickly started, the traditional reforming reactor only heats the reforming chamber and the purifying chamber through the electric heating, and the hydrogen production power generation equipment is generally applied to a field environment, so that the condition of lack of electricity exists, the power of the electric heating plate or the electric heating rod is small, the power consumption influence is exerted, the starting time is very slow, and the condition of the reaction temperature can be reached only about 10-24 hours; in addition, the reforming reaction process belongs to a process with lower heat requirement, and is carried out by being directly arranged in a reaction tube array in a reforming shell, so that the invention can not only efficiently meet the heating requirement of methanol water vaporization, but also reduce energy consumption; meanwhile, the reforming chamber and the reforming reaction coil pipe in the prior art are heated uniformly by adopting an aluminum casting process, the complex aluminum casting process greatly increases the equipment cost, and the material cost is higher; the side surface of the reforming shell is provided with the vertical flame guide groove, and the flame guide groove is used for guiding flame generated by the combustion chamber to the purification chamber so as to heat the purification chamber, so that the purification chamber is prevented from being electrically heated for a long time, the internal consumption is reduced, and the overall performance is higher.
As an improvement of the invention, a first buffer tank and a second buffer tank are arranged between the hot fluid outlet of the heat exchanger and the hydrogen inlet of the hydrogen fuel cell, the hot fluid outlet of the heat exchanger is communicated with the hydrogen inlet of the hydrogen fuel cell after passing through the first buffer tank and the second buffer tank in sequence through a pipeline, a first electromagnetic valve is arranged between the hot fluid outlet of the heat exchanger and the first buffer tank, and a second electromagnetic valve and a pressure reducing valve are arranged between the first buffer tank and the second buffer tank.
As an improvement of the invention, the reaction tube array comprises a plurality of steel tubes which are inserted between two side walls of the reforming shell, an air inlet chamber communicated with the inlet ends of the plurality of steel tubes is arranged at the inlet end of the steel tubes on the outer side of the side walls of the reforming shell, an air outlet chamber communicated with the outlet ends of the plurality of steel tubes is arranged at the outlet end of the steel tubes, an air inlet is arranged on the air inlet chamber, the outlet end of the coil is communicated with the air inlet of the air inlet chamber, an air outlet is arranged on the air outlet chamber, and the hydrogen rich is conveyed to the purifying chamber from the air outlet of the air outlet chamber.
As an improvement of the invention, the bottom surface of the reforming shell is provided with a metal cover plate for fixedly sealing the coil pipe in the groove.
As an improvement of the invention, the purifying chamber comprises a purifying shell made of metal materials, a palladium tube purifier is arranged in the purifying shell, an electric heating plate for heating the palladium tube purifier is arranged on the purifying shell, aluminum alloy powder serving as a heat transfer medium is filled in the purifying shell, the outlet end of the reaction tube is communicated with the inlet end of the palladium tube purifier, and the pure hydrogen outlet end of the palladium tube purifier is communicated with the pure hydrogen outlet of the purifying chamber.
As an improvement of the invention, the combustion chamber comprises a burner, the burner is provided with a combustion concave cavity which is opened upwards, a flame distributor and an igniter are arranged in the combustion concave cavity, a plurality of uniformly distributed flame holes and fuel feeding pipes are arranged on the flame distributor, an air inlet is arranged at the bottom of the combustion concave cavity, and the air inlet is communicated with an outlet of a blower.
Further, a tail gas outlet is arranged on the purification shell and is communicated with a fuel feeding pipe of the flame distributor through a return pipe, and a flow limiting valve and an electromagnetic valve are arranged on the return pipe.
As an improvement of the invention, a preheating base is arranged below the combustion chamber in the sealed box body, a vaporizer is arranged on the preheating base, the vaporizer comprises a vaporizing tube, an upper metal block and a lower metal block, the vaporizing tube is embedded between the upper metal block and the lower metal block, a preheating electric heating rod is embedded on the upper metal block or the lower metal block, the inlet end of the vaporizing tube is communicated with a methanol water inlet, the outlet end of the vaporizing tube is communicated with a fuel feeding tube, an air inlet channel is arranged on the preheating base at a position corresponding to the air inlet of the combustion chamber, the outlet end of the air inlet channel is in butt joint with the air inlet, and the inlet end of the air inlet channel is communicated with the outlet of the blower through a pipeline.
As an improvement of the invention, a screen filter is arranged in the sealed box body, the screen filter comprises a filter shell, an air inlet and an air outlet are arranged on the filter shell, a filter element is arranged at the air inlet in the filter shell, an outlet screen is arranged at the air outlet, the air inlet of the filter shell is communicated with the outlet end of the reaction tube, and the air outlet of the filter shell is communicated with the inlet end of the palladium tube purifier.
Further, a maintenance plug is arranged at the bottom of the filtering shell.
As an improvement of the invention, the sealing box body is made of stainless steel metal, and the sealing box body is coated with heat insulation cotton.
Compared with the prior art, the invention has the following advantages:
the invention separates the methanol water vaporization process and the reforming reaction process in two stages, can efficiently meet the methanol water vaporization heating requirement, and adopts a mode that a combustion chamber, a reforming chamber and a purifying chamber are sequentially arranged in a stacked manner from bottom to top, thereby reducing the volume and the occupied space of the device, leading the reforming reaction hydrogen production device to be portable and enlarging the application range;
the reforming chamber and the purifying chamber are heated by the combustion chamber, the electric heating plate is started at the same time to heat the purifying chamber, the working temperature of the reforming chamber and the purifying chamber, namely the working temperature of reforming reaction and the purifying working temperature can be reached within about 20-25 minutes, and the rapid starting can be realized, while the traditional reforming reactor only heats the reforming chamber and the purifying chamber through the electric heating, and the hydrogen production power generation equipment is generally applied to the field environment, so that the condition of lack of electricity exists, the power of the electric heating plate or the electric heating rod is smaller, the power consumption influence is exerted, the starting time is very slow, and the condition of the reaction temperature can be reached within about 10-24 hours;
the reforming reaction process belongs to a process with lower heat requirement, and is carried out by being directly arranged in a reaction tube array in a reforming shell, so that the invention can not only efficiently meet the heating requirement of methanol water vaporization, but also reduce energy consumption;
meanwhile, the reforming chamber and the reforming reaction coil pipe in the prior art are heated uniformly by adopting an aluminum casting process, the complex aluminum casting process greatly increases the equipment cost, and the material cost is higher;
the side surface of the reforming shell is provided with the vertical flame guide groove, and the flame guide groove is used for guiding flame generated by the combustion chamber to the purification chamber so as to heat the purification chamber, so that the purification chamber is prevented from being electrically heated for a long time, the internal consumption is reduced, and the overall performance is higher.
Drawings
FIG. 1 is a schematic diagram of a methanol to hydrogen power generation system of the present invention;
FIG. 2 is a schematic diagram of a combustion chamber of a methanol to hydrogen power generation system of the present invention;
FIG. 3 is a schematic diagram of a reforming chamber of a methanol to hydrogen power generation system of the present invention;
FIG. 4 is a schematic diagram of a purification chamber of a methanol to hydrogen power generation system of the present invention;
FIG. 5 is a schematic diagram of a filter of the methanol to hydrogen power generation system of the present invention;
FIG. 6 is a schematic diagram of a preheating base of the methanol to hydrogen power generation system of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, if directional indications (such as up, down, left, right, front, and rear … …) are included in the embodiments of the present invention, the directional indications are merely used to explain the relative positional relationship, movement conditions, etc. between the components in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indications are correspondingly changed.
In addition, if there is a description of "first", "second", etc. in the embodiments of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
Examples
Referring to fig. 1 to 6, a power generation system for producing hydrogen from methanol includes a heat exchanger 100, a methanation reactor 80, a reforming hydrogen production device, and a hydrogen fuel cell 200; the reforming hydrogen production device comprises a sealed box body 10, wherein a combustion chamber 20, a reforming chamber 30 and a purifying chamber 40 are arranged in the sealed box body 10, the combustion chamber 20, the reforming chamber 30 and the purifying chamber 40 are sequentially arranged in a stacked manner from bottom to top, and the combustion chamber 20 is used for heating the reforming chamber 30 and the purifying chamber 40;
the sealed box body 10 is provided with a methanol water inlet and an air inlet, and the air inlet of the sealed box body 10 is communicated with the combustion chamber 20 through a pipeline to provide air;
the reforming chamber 30 comprises a reforming shell 31 made of metal materials, a groove 32 is arranged on the bottom surface of the reforming shell 31, a coil 33 for vaporization is embedded in the groove 32, a reaction tube 34 is arranged in the reforming shell 31, a catalyst for reforming reaction is embedded in the reaction tube 34, an electric heating rod 35 is embedded in the reforming shell 31, the inlet end of the coil 33 is communicated with a methanol water inlet, and the outlet end of the coil 33 is communicated with the inlet end of the reaction tube 34;
the methanol water undergoes reforming reaction in the reforming chamber 30 to generate hydrogen-rich gas, the hydrogen-rich gas is conveyed to the purifying chamber 40 from the outlet end of the reaction tube array 34, and the purifying chamber 40 purifies the hydrogen-rich gas to obtain pure hydrogen;
the side of the reforming shell 31 is provided with a vertical fire guiding groove 36, the fire guiding groove 36 conducts the purifying chamber 40 and the combustion chamber 20, the fire guiding groove 36 is used for guiding the flame generated by the combustion chamber 20 to the purifying chamber 40 so as to heat the purifying chamber, and the purifying chamber 40 is provided with an electric heating plate 70;
the purifying chamber 40 is provided with a pure hydrogen outlet, the pure hydrogen outlet is communicated with an air inlet of the methanation reactor 80, an air outlet of the methanation reactor 80 is communicated with a hot fluid inlet of the heat exchanger 100, and a hot fluid outlet of the heat exchanger 100 is communicated with a hydrogen inlet of the hydrogen fuel cell 200.
From the above, the invention utilizes the methanol water to generate the hydrogen-rich by reforming reaction in the reforming chamber, the hydrogen-rich is conveyed to the purifying chamber from the outlet end of the reaction tube array, the purifying chamber purifies the hydrogen-rich to obtain pure hydrogen, the methanation reactor carries out methanation treatment on the pure hydrogen, and CO possibly existing in the pure hydrogen are purified 2 Converting into methane, cooling the pure hydrogen by a heat exchanger, reducing the temperature of the pure hydrogen to normal temperature, and then delivering the pure hydrogen to a hydrogen fuel cell for power generation. And the methanol water is gasified in the coil pipe, and the gasified methanol water steam enters the reaction tube array to carry out reforming reaction under the action of the catalyst and generate hydrogen-rich (H) 2 ,CO,CO 2 ) The hydrogen-enriched gas is filtered by a filter to remove possible catalyst dust, and enters a purifying chamber, and the purifying chamber is used for purifying and separating the hydrogen-enriched gas to obtain high-purity hydrogen gas.
In addition, the reforming chamber adopts the reforming shell made of metal materials, then the methanol water vaporization process and the reforming reaction process are carried out in two stages, the methanol water vaporization process is carried out in the coil pipe, the coil pipe directly heats the coil pipe by utilizing the combustion chamber and the electric heating rod in a mode of being embedded in the groove on the bottom surface of the reforming shell, and the reforming chamber and the purifying chamber are sequentially arranged from bottom to top in a stacked mode, so that the methanol water vaporization heating requirement is efficiently met, the equipment volume and the occupied space can be reduced, and the hydrogen production equipment for the reforming reaction is portable and the application range is enlarged; the reforming chamber and the purifying chamber are heated by the combustion chamber, the electric heating plate is started at the same time to heat the purifying chamber, the working temperature of the reforming chamber and the purifying chamber, namely the working temperature of reforming reaction and the purifying working temperature can be reached within about 20-25 minutes, and the rapid starting can be realized, while the traditional reforming reactor only heats the reforming chamber and the purifying chamber through the electric heating, and the hydrogen production power generation equipment is generally applied to the field environment, so that the condition of lack of electricity exists, the power of the electric heating plate or the electric heating rod is smaller, the power consumption influence is exerted, the starting time is very slow, and the condition of the reaction temperature can be reached within about 10-24 hours; in addition, the reforming reaction process belongs to a process with lower heat requirement, and is carried out by being directly arranged in a reaction tube array in a reforming shell, so that the invention can not only efficiently meet the heating requirement of methanol water vaporization, but also reduce energy consumption; meanwhile, the reforming chamber and the reforming reaction coil pipe in the prior art are heated uniformly by adopting an aluminum casting process, the complex aluminum casting process greatly increases the equipment cost, and the material cost is higher; the side surface of the reforming shell is provided with the vertical flame guide groove, and the flame guide groove is used for guiding flame generated by the combustion chamber to the purification chamber so as to heat the purification chamber, so that the purification chamber is prevented from being electrically heated for a long time, the internal consumption is reduced, and the overall performance is higher.
In this embodiment, a first buffer tank 300 and a second buffer tank 400 are disposed between the hot fluid outlet of the heat exchanger 100 and the hydrogen inlet of the hydrogen fuel cell 200, the hot fluid outlet of the heat exchanger 100 is sequentially connected to the hydrogen inlet of the hydrogen fuel cell 200 through the first buffer tank 300 and the second buffer tank 400 by a pipeline, a first electromagnetic valve 101 is disposed between the hot fluid outlet of the heat exchanger 100 and the first buffer tank 300, and a second electromagnetic valve 103 and a pressure reducing valve 102 are disposed between the first buffer tank 300 and the second buffer tank 400. The heat exchanger reduces the temperature of pure hydrogen to normal temperature and then the pure hydrogen enters the first buffer tank, in the actual power generation process, in order to ensure smooth power generation and meet the use requirement, the rated value of hydrogen produced by the reforming hydrogen production device is larger than 20% of the rated requirement of the hydrogen fuel cell, so that redundant hydrogen can be filled in the first buffer tank, when the hydrogen pressure of the first buffer tank reaches 24psi, the reforming hydrogen production device stops producing hydrogen, the hydrogen of the first buffer tank enters the second buffer tank after passing through the pressure reducing valve, once the hydrogen pressure of the second buffer tank reaches the highest pressure required by the hydrogen fuel cell, the second electromagnetic valve is closed, and the second electromagnetic valve is opened when the hydrogen pressure of the second buffer tank is lower than the lowest pressure required by the hydrogen fuel cell, so that the hydrogen pressure and flow requirement of the hydrogen fuel cell are not only met, but also can not be discharged into the atmosphere when the reforming hydrogen production device produces redundant hydrogen and stored in the first buffer tank, and the utilization efficiency of the hydrogen is improved.
In this embodiment, the reaction tube array 34 includes a plurality of steel tubes 341, the steel tubes 341 are inserted between two side walls of the reforming shell 31, an air inlet chamber 342 communicated with the inlet ends of the plurality of steel tubes 341 is disposed at the inlet end of the steel tubes 341 on the outer side of the side walls of the reforming shell 30, an air outlet chamber 344 communicated with the outlet ends of the plurality of steel tubes 341 is disposed at the outlet end of the steel tubes 341, an air inlet 343 is disposed on the air inlet chamber 342, the outlet end of the coil 33 is communicated with the air inlet 343 of the air inlet chamber 342, an air outlet 345 is disposed on the air outlet chamber 344, and the hydrogen rich gas is conveyed from the air outlet 345 of the air outlet chamber 344 to the purifying chamber 40. The reaction tubulation adopts the form of a plurality of steel pipes, is favorable to increasing reforming reaction area, improves the hydrogen-rich output of unit time promptly, and the inlet chamber can carry out evenly distributed to the vaporization methanol water that enters into the steel pipe, and the output is carried out the unified gathering of hydrogen-rich after the reforming reaction again to the outlet chamber. In this embodiment, the seal case and the reforming case are both made of aluminum.
In this embodiment, the bottom surface of the reforming housing 31 is provided with a metal cover plate 37 that fixedly seals the coil 33 within the groove 32. The metal cover plate can improve the heating uniformity of the coil when being heated by the combustion chamber.
In this embodiment, the purifying chamber 40 includes a purifying housing 41 made of metal, a palladium tube purifier 42 is disposed in the purifying housing 41, an electric heating plate 70 for heating the palladium tube purifier is disposed on the purifying housing 41, aluminum alloy powder 43 as a heat transfer medium is filled in the purifying housing 41, an outlet end of the reaction tube 34 is communicated with an inlet end 44 of the palladium tube purifier 42, and a pure hydrogen outlet end 45 of the palladium tube purifier 42 is communicated with a pure hydrogen outlet of the purifying chamber 40. The metal material is aluminum, and the aluminum alloy powder is filled in the purifying shell to serve as a heat conducting material, so that the palladium tube purifier is heated uniformly and rapidly; meanwhile, the damage to the palladium tube caused by direct flame heating or other hard contact (expansion with heat and contraction with cold) is avoided, the palladium tube can be heated uniformly, the heating mode of the palladium tube is greatly improved, the service life of the palladium tube purifier is about half a year by adopting the traditional flame heating mode, and the service life of the palladium tube purifier is 3 to 5 years by adopting the heating mode of the invention; and the aluminum alloy powder is filled in the purification shell, so that the cost of equipment materials and the processing cost can be reduced, and the economic benefit is improved.
In this embodiment, the combustion chamber 20 includes a burner 21, the burner 21 is provided with a combustion cavity 22 that is open upwards, a flame distributor 24 and an igniter 27 are disposed in the combustion cavity 22, a plurality of uniformly distributed flame holes 25 and a fuel feeding pipe 26 are disposed on the flame distributor 24, an air inlet 23 is disposed at the bottom of the combustion cavity 22 of the burner 21, and the air inlet 23 is communicated with an outlet of the blower 90. The flame distributor can uniformly heat the reforming chamber by uniformly distributing a plurality of flame holes.
In this embodiment, the purifying housing 41 is provided with an exhaust outlet 46, the exhaust outlet 46 is communicated with the fuel feed pipe 26 of the flame distributor 24 through the return pipe 14, and the return pipe 14 is provided with a flow limiting valve 15 and a solenoid valve 16. Tail gas (H) from the purification chamber 2 ,CO,CO 2 ) And the heat generated by combustion is supplied to the reactor as a subsequent heat source.
In this embodiment, a preheating base 60 is disposed below the combustion chamber 20 in the sealed case 10, a vaporizer is disposed on the preheating base 60, the vaporizer includes a vaporizing tube 83, an upper metal block 82 and a lower metal block 81, the vaporizing tube 83 is embedded between the upper metal block 82 and the lower metal block 81, a preheating electric heating rod 84 is embedded on the upper metal block 82 or the lower metal block 81, an inlet end of the vaporizing tube 83 is communicated with a methanol water inlet, an outlet end of the vaporizing tube 83 is communicated with the fuel feeding tube 26, an air inlet channel 61 is opened at a position corresponding to an air inlet 23 of the combustion chamber 20 on the preheating base 60, an outlet end of the air inlet channel 61 is in butt joint communication with the air inlet 23, and an inlet end of the air inlet channel 61 is communicated with an outlet of a blower 90 through a pipeline. The methanol water is used as fuel of the combustion chamber, and the vaporizer can heat the methanol water, so that the methanol water can enter the combustion chamber for combustion without complete vaporization, and the purpose is to quickly heat the reforming chamber and the purifier by flame to reach the temperature required by the work during the start-up of cold start, and the process only needs 20-25 minutes, so that the start-up time is greatly reduced. In the embodiment, the preheating base is made of ceramic materials, and the ceramic materials have the advantages of good heat transfer performance, low cost and the like.
In this embodiment, the methanol-water inlet includes a first methanol-water inlet and a second methanol-water inlet, the first methanol-water inlet is connected to the inlet end of the coil 33, the second methanol-water inlet is connected to the inlet end of the vaporizing tube 83, the first methanol-water inlet and the second methanol-water inlet are respectively provided with a methanol-water inlet pipe 12, and the methanol-water inlet pipe 12 is provided with an electromagnetic valve 13.
In this embodiment, a screen filter 50 is disposed in the sealed box 10, the screen filter 50 includes a filter housing 51, an air inlet 52 and an air outlet 53 are disposed on the filter housing 51, a filter element 54 is disposed in the filter housing 51 at the air inlet 52, an outlet screen 55 is disposed at the air outlet 53, the air inlet 52 of the filter housing 51 is communicated with the outlet end of the reaction column tube 34, and the air outlet 53 of the filter housing 51 is communicated with the inlet end 44 of the palladium tube purifier 42. The hydrogen-rich produced in the reforming chamber is filtered by a screen filter to remove catalyst dust which may exist, and then enters a palladium tube purifier. The bottom of the filtering shell is provided with a maintenance plug which is detachable and used for maintenance (maintenance is carried out once in 1-2 years according to the quality of the catalyst), and dust extracted from the filtering shell can be used for analysis and improvement of the catalyst.
In this embodiment, the sealing box 10 is made of stainless steel metal, and the periphery of the sealing box 10 is covered with heat insulation cotton 11. The high-temperature heat-insulating cotton prevents heat loss, and can effectively reduce the starting time.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. The utility model provides a methyl alcohol hydrogen generation power generation system which characterized in that: comprises a heat exchanger, a methanation reactor, a reforming hydrogen production device and a hydrogen fuel cell; the reforming hydrogen production device comprises a sealed box body, wherein a combustion chamber, a reforming chamber and a purifying chamber are arranged in the sealed box body, the combustion chamber, the reforming chamber and the purifying chamber are sequentially arranged in a stacked manner from bottom to top, and the combustion chamber is used for heating the reforming chamber and the purifying chamber; the sealed box body is provided with a methanol water inlet and an air inlet, and the air inlet of the sealed box body is communicated with the combustion chamber through a pipeline to provide air; the reforming chamber comprises a reforming shell made of metal materials, a groove is formed in the bottom surface of the reforming shell, a coil pipe for vaporization is embedded in the groove, a reaction tube is arranged in the reforming shell, a catalyst for reforming reaction is arranged in the reaction tube, an electric heating rod is embedded in the reforming shell, the inlet end of the coil pipe is communicated with a methanol water inlet, and the outlet end of the coil pipe is communicated with the inlet end of the reaction tube; the methanol water is subjected to reforming reaction in the reforming chamber to generate hydrogen-rich gas, the hydrogen-rich gas is conveyed to the purifying chamber from the outlet end of the reaction tube array, and the purifying chamber is used for purifying the hydrogen-rich gas to obtain pure hydrogen; the side surface of the reforming shell is provided with a vertical fire guiding groove, the fire guiding groove is used for conducting the purification chamber and the combustion chamber, the fire guiding groove is used for guiding flame generated by the combustion chamber to the purification chamber so as to heat the purification chamber, and the purification chamber is provided with an electric heating plate; the purifying chamber is provided with a pure hydrogen outlet which is communicated with an air inlet of the methanation reactor, an air outlet of the methanation reactor is communicated with a hot fluid inlet of the heat exchanger, and a hot fluid outlet of the heat exchanger is communicated with a hydrogen inlet of the hydrogen fuel cell;
a metal cover plate for fixedly sealing the coil pipe in the groove is arranged on the bottom surface of the reforming shell;
the sealed box body is made of stainless steel metal, and heat insulation cotton is coated on the outer periphery of the sealed box body.
2. The methanol to hydrogen generation power generation system of claim 1 wherein: the hot fluid outlet of the heat exchanger is communicated with the hydrogen inlet of the hydrogen fuel cell after sequentially passing through the first buffer tank and the second buffer tank through a pipeline, a first electromagnetic valve is arranged between the hot fluid outlet of the heat exchanger and the first buffer tank, and a second electromagnetic valve and a pressure reducing valve are arranged between the first buffer tank and the second buffer tank.
3. The methanol to hydrogen generation power generation system of claim 1 wherein: the reaction tube array comprises a plurality of steel tubes, the steel tubes are inserted between two side walls of the reforming shell, an air inlet chamber communicated with the inlet ends of the plurality of steel tubes is arranged at the inlet end of the steel tubes on the outer side of the side walls of the reforming shell, an air outlet chamber communicated with the outlet ends of the plurality of steel tubes is arranged at the outlet end of the steel tubes, an air inlet is arranged on the air inlet chamber, the outlet end of the coil is communicated with the air inlet of the air inlet chamber, an air outlet is arranged on the air outlet chamber, and hydrogen is conveyed to the purification chamber from the air outlet of the air outlet chamber.
4. The methanol to hydrogen generation power generation system of claim 1 wherein: the purifying chamber comprises a purifying shell made of metal materials, a palladium tube purifier is arranged in the purifying shell, an electric heating plate for heating the palladium tube purifier is arranged on the purifying shell, aluminum alloy powder serving as a heat transfer medium is filled in the purifying shell, the outlet end of the reaction tube array is communicated with the inlet end of the palladium tube purifier, and the pure hydrogen outlet end of the palladium tube purifier is communicated with the pure hydrogen outlet of the purifying chamber.
5. The methanol to hydrogen generation power generation system of claim 4 wherein: the combustion chamber comprises a combustor, the combustor is provided with a combustion concave cavity which is opened upwards, a flame distributor and an igniter are arranged in the combustion concave cavity, a plurality of uniformly distributed flame holes and a fuel feeding pipe are arranged on the flame distributor, an air inlet is formed in the bottom of the combustion concave cavity, and the air inlet is communicated with an outlet of the air blower.
6. The methanol to hydrogen generation power generation system of claim 5 wherein: the purification shell is provided with a tail gas outlet which is communicated with a fuel feed pipe of the flame distributor through a return pipe, and the return pipe is provided with a flow limiting valve and an electromagnetic valve.
7. The methanol to hydrogen generation power generation system of claim 5 wherein: the utility model discloses a combustion chamber, including sealed box, combustion chamber, preheating base, air inlet passageway's exit end and air inlet butt joint intercommunication, the air inlet passageway's entrance end is linked together through the export of pipeline and air-blower, the below at the combustion chamber is equipped with the preheating base in the sealed box, be equipped with the vaporizer on the preheating base, the vaporizer includes the vaporization pipe, go up metal block and lower metal block, the vaporization pipe is embedded between last metal block and lower metal block, go up metal block or lower metal block is last to be embedded to have the preheating electric heater rod, the entrance end of vaporization pipe is linked together with the methanol water inlet, the exit end of vaporization pipe is linked together with the fuel inlet pipe, the preheating base is opened in the air inlet of combustion chamber and is had the air inlet butt joint intercommunication, the exit end of air inlet passageway is linked together through the pipeline and the export of air-blower.
8. The methanol to hydrogen generation power generation system of claim 4 wherein: the utility model discloses a palladium tube purifier, including the sealed box, be equipped with screen cloth filter in the sealed box, screen cloth filter includes the filtration casing, is equipped with air inlet and gas outlet on the filtration casing, is equipped with the filter core in the air inlet department of filtration casing, is equipped with the export screen cloth in gas outlet department, and the air inlet of filtration casing is linked together with the exit end of reaction tubulation, and the gas outlet of filtration casing is linked together with the entrance point of palladium tube purifier.
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| CN111313059A (en) * | 2020-03-26 | 2020-06-19 | 广东能创科技有限公司 | Methanol-water hydrogen fuel cell generator |
| CN111509279B (en) * | 2020-04-30 | 2021-06-22 | 郑州帅先新能源科技有限公司 | In-situ hydrogen production fuel cell system |
| CN111453698A (en) * | 2020-05-14 | 2020-07-28 | 广东能创科技有限公司 | Small-size hydrogenation station of methanol-water |
| CN111453699B (en) * | 2020-05-22 | 2021-08-31 | 力行氢能科技股份有限公司 | Hydrogen production and hydrogen purification device |
| CN111573622A (en) * | 2020-05-25 | 2020-08-25 | 广东能创科技有限公司 | Thermoelectric generation self-powered methanol-water reforming hydrogen production system |
| CN111908423A (en) * | 2020-05-25 | 2020-11-10 | 广东能创科技有限公司 | Thermoelectric power generation coupling methanol-water reforming hydrogen production power generation system |
| CN111987782A (en) * | 2020-08-07 | 2020-11-24 | 强伟氢能科技有限公司 | Methanol reforming hydrogen production power generation system applied to VR equipment |
| CN114436210B (en) * | 2022-03-07 | 2023-08-11 | 广东工业大学 | High-efficient integrated distributed methanol reforming hydrogen production purification system |
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