CN117599691A - Hydrogen production device by methanol-water reforming - Google Patents

Hydrogen production device by methanol-water reforming Download PDF

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Publication number
CN117599691A
CN117599691A CN202311595460.9A CN202311595460A CN117599691A CN 117599691 A CN117599691 A CN 117599691A CN 202311595460 A CN202311595460 A CN 202311595460A CN 117599691 A CN117599691 A CN 117599691A
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China
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reforming
methanol
chamber
storage tank
reaction
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Chinese (zh)
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马丁
刘兴武
高子睿
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Peking University
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Peking University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
    • 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
    • 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
    • C01B2203/1288—Evaporation of one or more of the different feed components

Abstract

The embodiment of the application provides a methanol-water reforming hydrogen production device, which comprises a box body, a reforming reactor and a heating module, wherein the interior of the box body is divided into a reforming chamber and a heating chamber, and the reforming chamber is a closed cavity; the reforming reactor is positioned in the reforming chamber and comprises a plurality of reaction tubes which are arranged in an array, and the reaction tubes are filled with catalysts; the heating module comprises a liquid storage tank and a heat-conducting medium, wherein the liquid storage tank is positioned in the heating chamber and is used for storing the heat-conducting medium; the liquid storage tank is communicated with the reforming chamber so that the heat conducting medium flows into the reforming chamber and is filled between the reaction tubes and the inner wall of the reforming chamber, and the heat conducting medium is used for providing heat for reforming reaction. The methanol-water reforming hydrogen production device can have the advantages of miniaturization and high catalytic efficiency, and is beneficial to promoting popularization and application of the methanol-water steam reforming hydrogen production technology in miniaturized hydrogen production scenes.

Description

Hydrogen production device by methanol-water reforming
Technical Field
The application relates to the technical field of hydrogen production, in particular to a methanol-water reforming hydrogen production device.
Background
The energy crisis and environmental pollution problems faced by human beings are increasingly serious. The hydrogen energy is widely paid attention to due to the advantages of high combustion heat value, cleanness, environmental protection and the like. In recent years, proton exchange membrane fuel cell (Proton Exchange Membrane Fuel Cell, abbreviated as PEMFC) technology using pure hydrogen as fuel has been basically mature.
The pure hydrogen used in the fuel cell at present mainly comes from the high-pressure hydrogen storage and reforming hydrogen production technologies. The volume energy density of the high-pressure hydrogen storage is lower, the cost is higher, the construction of the hydrogen adding station is imperfect, and the popularization and the application of the fuel cell are limited. Compared with the high-pressure hydrogen storage technology, the reforming hydrogen production technology, in particular to the liquid fuel reforming hydrogen production technology, has higher volume energy density and is easier to store and transport.
Methanol has been widely studied in the field of reforming hydrogen production because of its higher hydrogen to carbon ratio and lower reforming temperature. At present, a large number of technologies for preparing hydrogen by reforming methanol and steam are applied, specifically, methanol and steam pass through a catalyst under certain temperature and pressure conditions, and under the action of the catalyst, methanol cracking reaction and water vapor shift reaction of carbon monoxide are carried out to generate hydrogen and carbon dioxide.
However, the research of the methanol-water reforming hydrogen production device in the related technology is in a starting stage, has the problems of large volume, low catalytic efficiency and the like, and is not beneficial to the popularization and application of the methanol-water reforming hydrogen production technology in a miniaturized hydrogen production scene.
Disclosure of Invention
An object of an embodiment of the present application is to provide a methanol-water reforming hydrogen generating apparatus, so as to achieve miniaturization of the methanol-water reforming hydrogen generating apparatus and improvement of catalytic efficiency. The specific technical scheme is as follows:
the embodiment of the application provides a methanol-water reforming hydrogen production device, which comprises a box body, a reforming reactor and a heating module, wherein the box body is provided with a base, the interior of the box body is divided into a reforming chamber and a heating chamber, and the reforming chamber is a closed cavity; the reforming reactor is positioned in the reforming chamber and comprises a plurality of reaction tubes which are arranged in an array manner, and the reaction tubes are filled with catalysts; the side wall of the reforming chamber is provided with a raw material inlet and a gas outlet, the reforming reactor is respectively communicated with the raw material inlet and the gas outlet, the raw material inlet is used for feeding methanol and water into the reforming reactor, the gas outlet is used for feeding gas generated after reforming reaction to flow out, and the gas comprises hydrogen and carbon dioxide; the heating module comprises a liquid storage tank and a heat conducting medium, wherein the liquid storage tank is positioned in the heating chamber and is used for storing the heat conducting medium; the liquid storage tank is communicated with the reforming chamber so that the heat conducting medium flows into the reforming chamber and is filled between the reaction tubes and the inner wall of the reforming chamber, and the heat conducting medium is used for providing heat for reforming reaction.
In some embodiments of the present application, the reforming reactor comprises a plurality of reaction sets arranged in parallel, each reaction set comprising a plurality of the reaction tubes arranged in series.
In some embodiments of the present application, the reforming reactor further comprises a total inlet line in communication with the feedstock inlet and a total outlet line in communication with the gas outlet, each of the reaction sets in communication with the total inlet line and the total outlet line, respectively.
In some embodiments of the present application, the reaction cuvettes comprise a tube body and adapters at both ends of the tube body, the adapters being in communication with the main inlet line or the main outlet line or an adjacent adapter of the reaction cuvettes via a conduit.
In some embodiments of the present application, the heating module further comprises a burner disposed at the base and below the reservoir; the side wall of the base is provided with a fuel inlet which is communicated with the combustion furnace, and the combustion furnace is used for combusting fuel to heat the heat conducting medium in the liquid storage tank.
In some embodiments of the present application, the fuel for heating the heat transfer medium is methanol; an air inlet is formed in the bottom of the side wall of the heating chamber and used for allowing air to enter; an exhaust channel is arranged above the liquid storage tank and used for discharging high-temperature gas generated after combustion.
In some embodiments of the present application, a methanol vaporizer is further disposed inside the base, the methanol vaporizer is provided with a curved flow channel, one end of the curved flow channel is communicated with the fuel inlet, and the other end of the curved flow channel is communicated with the combustion furnace; the base is also provided with a heating rod, and the heating rod is used for heating the methanol flowing through the curved flow channel so as to enable the methanol to be heated and vaporized.
In some embodiments of the present application, the heating module further comprises a circulation pump, the circulation pump being located within the heating chamber; one end of the liquid storage tank is communicated with the reforming chamber through the circulating pump, and the other end of the liquid storage tank is communicated with the reforming chamber through a pipeline.
In some embodiments of the present application, the circulation pump is located above the liquid storage tank and is in communication with a top end of the liquid storage tank, and the circulation pump is configured to re-pump the heat transfer medium flowing through the reforming chamber into the liquid storage tank.
In some embodiments of the present application, a heat-conducting medium outlet is formed in a side wall of the reforming chamber, and a heat-conducting medium inlet is formed in a side wall of the heat supply chamber; the heat conducting medium outlet is higher than the heat conducting medium inlet, and is communicated with the heat conducting medium inlet through a pipeline arranged outside the box body; the inlet end of the circulating pump is communicated with the heat conducting medium inlet, and the outlet end of the circulating pump is communicated with the top of the liquid storage tank; the top of the reforming chamber is also provided with a filling port, and the filling port is used for filling or replacing the heat-conducting medium; the heat conducting medium is high-temperature heat conducting oil.
The methanol-water reforming hydrogen production device comprises a box body, wherein the box body can provide installation space and protection effect for a reforming reactor and a heating module, raw materials required by reforming reaction, namely methanol and aqueous solution, can enter the reforming reactor through a raw material inlet, methanol and water flow through a catalyst reaction bed layer in the reforming reactor to carry out reforming reaction process, hydrogen and carbon dioxide are generated, and the generated hydrogen and carbon dioxide can flow out of the box body through a gas outlet and enter a downstream hydrogen utilization module. In this application embodiment, the reforming reactor includes a plurality of reaction tubulars, and a plurality of reaction tubulars are assembled into the array and are arranged in the reforming chamber, from this, the structure of reforming reactor is compacter, and the volume is less to be favorable to improving volume utilization and heat exchange efficiency, reduce whole reforming hydrogen production device's volume and heat energy dissipation. In addition, in this application embodiment, the reforming chamber is airtight cavity, through introducing the heat conduction medium into the reforming chamber to fill between each reaction tubulation and between the inner wall of reaction tubulation and reforming chamber, can make the reforming reactor submerge in the heat conduction medium completely, thereby make the heat exchange between heat conduction medium and each reaction tubulation more abundant and even, realize the even heating of the catalyst bed in the reaction tubulation, improve the operating stability of catalyst, and then be favorable to improving catalytic efficiency. Therefore, the methanol-water reforming hydrogen production device disclosed by the embodiment of the application can have the advantages of miniaturization and high catalytic efficiency, and is beneficial to promoting popularization and application of the methanol-water steam reforming hydrogen production technology in miniaturized hydrogen demand and hydrogen production scenes.
Of course, not all of the above-described advantages need be achieved simultaneously in practicing any one of the products or methods of the present application.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following description will briefly introduce the drawings that are required to be used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other embodiments may also be obtained according to these drawings to those skilled in the art.
FIG. 1 is a schematic view showing the external structure of a hydrogen-producing apparatus for reforming methanol-water according to an embodiment of the present application;
FIG. 2 is a schematic view showing the internal structure of the hydrogen-producing apparatus for reforming methanol-water shown in FIG. 1;
FIG. 3 is a cross-sectional view of the methanol-water reforming hydrogen-producing apparatus shown in FIG. 1 in a height direction;
fig. 4 is a left side view of the methanol-water reforming hydrogen-producing apparatus shown in fig. 1.
FIG. 5 is a rear view of the methanol-water reforming hydrogen-producing unit of FIG. 1;
FIG. 6 is a right side view of the methanol-water reforming hydrogen-producing unit of FIG. 1;
FIG. 7 is a top view of the methanol-water reforming hydrogen-producing unit of FIG. 1;
fig. 8 is a schematic view of a methanol vaporizer inside the base of fig. 1.
In the figure: a methanol-water reforming hydrogen-producing unit 10; a case 100; a base 110; a fuel inlet 111; a reforming chamber 120; a raw material inlet 121; a gas outlet 122; a heat transfer medium outlet 123; a fill port 124; a heat supply chamber 130; an air inlet 131; an exhaust passage 132; a heat transfer medium inlet 133; a reforming reactor 200; a reaction set 210; a reaction column tube 211; a tube body portion 2111; an adapter 2112; a clasp 212; a main inlet line 213; a main outlet line 214; a connection pipe 215; a heating module 300; a liquid storage tank 310; a combustion furnace 320; a methanol vaporizer 330; a curved flow path 331; a line 340; a heating rod 400; thermocouple 500.
Detailed Description
The following description of the embodiments of the present application 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, of the embodiments of the present application. Based on the embodiments herein, a person of ordinary skill in the art would be able to obtain all other embodiments based on the disclosure herein, which are within the scope of the disclosure herein.
As to the background art, the research of the methanol-water reforming hydrogen production device in the related art is in the starting stage, has the problems of large volume, low catalytic efficiency and the like, and is not beneficial to the popularization and application of the methanol-water steam reforming hydrogen production technology in miniaturized hydrogen-producing scenes.
In view of this, embodiments of the present application provide a methanol-to-water reformate hydrogen plant 10. Referring to fig. 1 to 4, wherein fig. 1 is a schematic view showing an external structure of a methanol-water reforming hydrogen-producing apparatus 10 according to an embodiment of the present application; FIG. 2 is a schematic diagram showing the internal structure of the hydrogen-producing apparatus 10 for reforming methanol-water shown in FIG. 1; FIG. 3 is a cross-sectional view of the methanol-water reforming hydrogen-producing apparatus 10 shown in FIG. 1 in a height direction; fig. 4 is a left side view of the methanol-water reforming hydrogen-producing apparatus 10 shown in fig. 1.
As shown in fig. 1 to 4, in the embodiment of the present application, the methanol-water reforming hydrogen generating apparatus 10 includes a case 100, a reforming reactor 200, and a heating module 300, wherein the case 100 has a base 110, and an interior of the case 100 is partitioned into a reforming chamber 120 and a heating chamber 130, and the reforming chamber 120 is a closed cavity. The reforming reactor 200 is located in the reforming chamber 120, and the reforming reactor 200 includes a plurality of reaction tubes 211 arranged in an array, and the reaction tubes 211 are filled with a catalyst; the reforming chamber 120 is provided with a raw material inlet 121 and a gas outlet 122 on a side wall thereof, the reforming reactor 200 is respectively communicated with the raw material inlet 121 and the gas outlet 122, the raw material inlet 121 is used for feeding methanol and water into the reforming reactor 200, and the gas outlet 122 is used for feeding out gas generated after the reforming reaction, and the gas comprises hydrogen and carbon dioxide. The heating module 300 comprises a liquid storage tank 310 and a heat-conducting medium, wherein the liquid storage tank 310 is positioned in the heat supply chamber 130 and is used for storing the heat-conducting medium; the liquid storage tank 310 communicates with the reforming chamber 120 so that a heat transfer medium flows into the reforming chamber 120 and fills between the reaction tubes 211 and the inner wall of the reforming chamber 120, and the heat transfer medium is used to supply heat for the reforming reaction.
The methanol-water reforming hydrogen generating device 10 of the present embodiment includes a case 100, the case 100 can provide an installation space and a protection function for the reforming reactor 200 and the heating module 300, raw materials required for the reforming reaction, that is, methanol and aqueous solution, can enter the reforming reactor 200 through the raw material inlet 121, and in the reforming reactor 200, methanol and water flow through the catalyst reaction bed layer to perform a reforming reaction process, generate hydrogen and carbon dioxide, and the generated hydrogen and carbon dioxide can flow out of the case 100 through the gas outlet 122 and enter the downstream hydrogen module. In the embodiment of the present application, the reforming reactor 200 includes a plurality of reaction tubes 211, and the plurality of reaction tubes 211 are assembled into an array and placed in the reforming chamber 120, so that the structure of the reforming reactor 200 is more compact and the volume is smaller, thereby being beneficial to improving the volume utilization rate and the heat exchange efficiency and reducing the volume and the heat dissipation of the whole reforming hydrogen-generating device. In addition, in the embodiment of the present application, the reforming chamber 120 is a closed cavity, and the heat-conducting medium is introduced into the reforming chamber 120 and filled between the reaction tubes 211 and the inner wall of the reforming chamber 120, so that the reforming reactor 200 is completely immersed in the heat-conducting medium, and heat exchange between the heat-conducting medium and the reaction tubes 211 is more sufficient and uniform, so that uniform heating of the catalyst bed in the reaction tubes 211 is achieved, and the operation stability of the catalyst is improved, thereby being beneficial to improving the catalytic efficiency. Therefore, the methanol-water reforming hydrogen production device 10 of the embodiment of the application can have the advantages of miniaturization and high catalytic efficiency, and is beneficial to promoting popularization and application of the methanol-water steam reforming hydrogen production technology in miniaturized hydrogen demand and hydrogen production scenes.
In the embodiment of the present application, the reforming chamber 120 and the heating chamber 130 may be disposed in parallel, and may occupy half of the volume of the case 100, respectively. The raw material inlet 121 and the gas outlet 122 arranged on the box body 100 are reserved metric interfaces.
The catalyst packed in the reaction tube 211 may be a copper-based catalyst, for example CuZnAl, cuZnZr, cuZr, cuCeZr, cuCe, etc. The present application is not limited to the type of catalyst. Before the catalyst is completely filled and applied to the hydrogen production process, the catalyst can be subjected to one-time activation treatment, for example, treatment for 2-6 hours at 200-400 ℃ with 10% -100% of hydrogen and nitrogen. After the activation treatment, methanol and water may be pumped into the reforming reactor 200 by a liquid pump to perform a reforming reaction.
When adding the raw materials, methanol and water may be mixed first, and then the mixed solution may be directly pumped into the reforming reactor 200; it is also possible to place methanol and water in two separate tanks, respectively, and then pump the methanol and water into a merging pipe, respectively, by two liquid pumps, where the methanol and water merge and then enter the reforming reactor 200. Thus, the methanol and the water can be stored independently, which is convenient for other applications of the methanol and the water, and in addition, the real-time mixing proportion of the methanol and the water can be conveniently adjusted through the flow rate of the liquid pump. The present application is not limited in this regard.
As shown in fig. 2 and 3, in the embodiment of the present application, the reforming reactor 200 includes a plurality of reaction groups 210 arranged in parallel, each reaction group 210 including a plurality of reaction tubes 211 arranged in series, the reaction tubes 211 extending in the height direction of the reforming chamber 120. Thus, on the one hand, the space in the reforming chamber 120 can be fully utilized to make the whole reforming reactor 200 smaller in size, and on the other hand, the cross section of each reaction tube 211 can be smaller, so that the tight filling of the catalyst is conveniently realized, the filling mode of the catalyst is optimized, and further, the reactants can be forced to flow through the catalyst bed layer, and the catalyst utilization efficiency is improved.
Further, the outer circumferential surface of each reaction tube 211 may be wrapped by two opposite buckles 212 and then connected with the adjacent reaction tube 211 by the buckles 212 to be assembled into an array. Each reaction column 211 includes a tube body 2111 and adapters 2112 at both ends of the tube body 2111, and the adapters 2112 may communicate with the adapters 2112 of the adjacent reaction columns 211 through the connection tube 215, thereby realizing the serial connection of the two reaction columns 211. Thus, the reaction tubes 211 are relatively independent, and can be easily assembled and disassembled when the catalyst is replaced. In addition, mixing and cascade filling of different types of catalysts can be realized, and richer catalytic performance and product selectivity optimization are realized. In a particular embodiment, both the adapter 2112 and the tube portion 2111 are standard parts, thereby facilitating replacement.
Further, as shown in fig. 2, the reforming reactor 200 further includes a main inlet line 213 and a main outlet line 214, the main inlet line 213 and the main outlet line 214 being located below each of the reaction trains 211, the main inlet line 213 being in communication with the raw material inlet 121, the main outlet line 214 being in communication with the gas outlet 122, and each of the reaction groups 210 being in communication with the main inlet line 213 and the main outlet line 214, respectively. Thus, a parallel aggregation of multiple reaction groups 210 is facilitated.
In a specific embodiment, the adaptor 2112 at the inlet of the first reaction column 211 in each reaction group 210 may be in communication with the main inlet line 213 via the connection pipe 215, and the adaptor 2112 at the outlet of the last reaction column 211 in each reaction group 210 may be in communication with the main outlet line 214 via the connection pipe 215, whereby each reaction group 210 may be in communication with the main inlet line 213 and the main outlet line 214, respectively.
In a specific embodiment, the reforming reactor 200 includes 4 reaction groups 210 arranged in parallel, each reaction group 210 is provided with 16 reaction columns 211 in series, that is, the reforming reactor 200 includes 64 reaction columns 211 in total, the total volume of the 64 reaction columns 211 is about 965ml, and the size of the reforming reactor 200 is about 452×360×190mm.
Experiments by the inventors have verified that by setting the reforming reactor 200 to the above specifications, complete catalytic conversion of methanol and water can be achieved with a conversion of over 99.9%, the converted product being mainly hydrogen and carbon dioxide (produced in a stoichiometric ratio of 3:1), the selectivity of carbon monoxide in the product being less than 0.001% (total outlet gas concentration), and no other gases being detected in the product. It has been demonstrated that the methanol-water reforming hydrogen generator 10 of the embodiment of the present application can ensure efficient, highly selective reforming of methanol and water to produce hydrogen while achieving miniaturization.
The number of reaction groups 210 and the number of reaction tubes 211 connected in series in each reaction group 210 are not limited, and in practical application, the length of the catalyst through which the raw material passes can be adjusted by adjusting the number of reaction tubes 211 connected in series in each reaction group 210, so that efficient catalytic performance and full conversion of the raw material are realized.
In the embodiment of the present application, the product generated by the reforming reaction includes hydrogen and carbon dioxide, which flow out through the gas outlet 122 of the reforming chamber 120, and the carbon dioxide has no influence on the downstream hydrogen module, so the hydrogen and the carbon dioxide may not be split. The hydrogen flowing out from the gas outlet 122 can be directly utilized, or the methanol-water reforming hydrogen generating device 10 in the embodiment of the present application can be used in series with a hydrogen fuel cell, a hydrogen internal combustion engine, or the like. The present application is not limited in this regard.
In the embodiment of the application, the heat required by the reforming reaction is derived from a heat conducting medium, and the heat conducting medium can be high-temperature heat conducting oil. The high-temperature heat conduction oil is one of heat conduction oil and is mainly applied to certain extra-high-temperature working environments. The heat conducting oil is used as a heat transfer medium, has the characteristics of uniform heating, good heat transfer effect, energy conservation, convenient transportation and operation and the like, and is widely applied to various occasions.
As shown in fig. 2 and 3, in the embodiment of the present application, the heating module 300 further includes a combustion furnace 320, where the combustion furnace 320 is disposed on the base 110 and below the liquid storage tank 310; the sidewall of the base 110 is provided with a fuel inlet 111, and the fuel inlet 111 communicates with a combustion furnace 320, and the combustion furnace 320 is used to burn fuel to heat the heat transfer medium in the liquid storage tank 310. In the embodiment of the present application, by providing the combustion furnace 320 and burning the fuel, heat can be generated, so as to heat the heat-conducting medium in the liquid storage tank 310, and the heated heat-conducting medium enters the reforming chamber 120 to provide heat for the reforming reaction.
Further, the fuel may be methanol. The hydrogen-producing raw material methanol is used as the fuel, so that the fuel is convenient to obtain. Specifically, in the embodiment of the present application, the methanol and water as raw materials may be separately placed in the storage tank, and when in use, the methanol is split, so that a part of the methanol and water are converged into the reforming reactor 200 to perform the reforming reaction process, and another part of the methanol enters the combustion furnace 320 to be combusted as fuel, so that no additional fuel is required to be provided for the heating module 300, thereby facilitating the acquisition and management of the fuel.
Referring to fig. 5-7, wherein fig. 5 is a rear view of the methanol-water reforming hydrogen-producing apparatus 10 shown in fig. 1; FIG. 6 is a right side view of the methanol-water reforming hydrogen-producing unit 10 of FIG. 1; fig. 7 is a top view of the methanol-water reforming hydrogen-producing apparatus shown in fig. 1.
As shown in fig. 1 to 7, the sidewall bottom of the heat supply chamber 130 is provided with an air inlet 131, and the air inlet 131 is used for air intake. An exhaust passage 132 is provided above the liquid storage tank 310, and the exhaust passage 132 is used for discharging high-temperature gas generated after combustion. By providing the air inlet 131 at the bottom of the sidewall of the heating chamber 130 and the air outlet 132 at the top of the heating chamber 130, a chimney effect can be generated, and air can be sucked into the heating chamber 130 to be mixed with methanol under the action of the chimney effect. The combustion furnace 320 may be an electric ignition device, and the mixed air and methanol are burned after the combustion furnace 320 is ignited, and the heat-conducting medium in the liquid storage tank 310 is heated, so that heat is provided for the reforming reaction through the heat-conducting medium. Therefore, the self-sufficiency of heat can be realized, and no additional heat source is needed.
In a specific embodiment, as shown in fig. 1, 5 and 6, the air inlets 131 are provided with three air inlets 131, and the three air inlets 131 are respectively located at the bottoms of three side walls of the heat supply chamber 130, and the air inlets 131 are elongated holes. Therefore, the air flow rate can be increased, sufficient oxygen is provided for the combustion of the methanol, and the sufficient combustion of the methanol is realized.
In other embodiments of the present application, the air inlet 131 may have other shapes, such as a round hole or a square hole, and the present application does not limit the shape of the air inlet 131.
Referring to fig. 8, fig. 8 is a schematic view of the structure of the methanol vaporizer 330 inside the base 110 shown in fig. 1.
As shown in fig. 8, a methanol vaporizer 330 is further provided inside the base 110, and the methanol vaporizer 330 is located below the reforming chamber 120. The methanol vaporizer 330 is provided with a curved flow passage 331, a passage is provided in the interior of the base 110, one end of the curved flow passage 331 is communicated with the fuel inlet 111 through the interior passage of the base 110, and the other end of the curved flow passage 331 is communicated with the combustion furnace 320 through the interior passage of the base 110; the base 110 is further provided with a heating rod 400, and the heating rod 400 is used for heating the methanol flowing through the curved flow passage 331 so as to vaporize the methanol by heating. In the embodiment of the application, by arranging the curved flow channel 331 and the heating rod 400, the methanol liquid entering the base 110 can be sufficiently heated to be vaporized, so that the vaporized methanol is conveniently sprayed out of the combustion furnace 320 and is sufficiently combusted.
It should be noted that, in the use process of the methanol-water reforming hydrogen generator 10 according to the embodiment of the present application, after the heated heat transfer medium enters the reforming chamber 120, the heat transfer medium may not only provide heat for the reforming reactor 200, but also provide heat for the methanol vaporizer 330 disposed below the reforming chamber 120, and at this time, it is considered that the heating rod 400 is turned off and the methanol is vaporized only by the heat provided by the heat transfer medium.
It is understood that in the embodiment of the present application, the bottom surface of the base 110 is provided with a sealing plate, and the methanol vaporizer 330 can be sealed by the sealing plate to prevent methanol leakage.
In the embodiment of the present application, the heating module 300 further includes a circulating pump (not illustrated in the drawings), and the circulating pump is located in the heat supply chamber 130; the liquid storage tank 310 is a hollow tank structure, one end of the liquid storage tank 310 is communicated with the reforming chamber 120 through a circulating pump, and the other end of the liquid storage tank 310 is communicated with the reforming chamber 120 through a pipeline 340. By providing the circulation pump, the heat transfer medium can be driven to circulate between the reforming chamber 120 and the liquid storage tank 310, and the utilization rate of the heat transfer medium can be improved.
Further, a circulation pump is disposed above the liquid storage tank 310 and communicates with the top end of the liquid storage tank 310, and the circulation pump is used to re-pump the heat transfer medium flowing through the reforming chamber 120 into the liquid storage tank 310. In consideration of the fact that the heat transfer medium flowing through the reforming chamber 120 has exchanged heat with the reforming reactor 200, the temperature thereof is low, and the material requirements for the circulation pump are correspondingly reduced, the circulation pump is disposed above the liquid storage tank 310, which is advantageous in reducing the cost of the circulation pump.
Specifically, as shown in fig. 1, a heat-conducting medium outlet 123 is formed in the side wall of the reforming chamber 120, and a heat-conducting medium inlet 133 is formed in the side wall of the heating chamber 130; the heat transfer medium outlet 123 is higher than the heat transfer medium inlet 133, and the heat transfer medium outlet 123 is communicated with the heat transfer medium inlet 133 through a pipe provided outside the case 100; the inlet end of the circulation pump is communicated with the heat conducting medium inlet 133, and the outlet end of the circulation pump is communicated with the top of the liquid storage tank 310.
In the embodiment of the present application, as shown in fig. 1 and 2, the bottom end of the liquid storage tank 310 and the reforming chamber 120 may be directly connected through a pipe 340. In the circulation process, the heat transfer medium flows into the reforming chamber 120 through the pipe 340 from the bottom end of the liquid storage tank 310, then exchanges heat with the reforming reactor 200 in the reforming chamber 120, then sequentially enters the circulation pump through the heat transfer medium outlet 123 and the heat transfer medium inlet 133, and finally reenters the liquid storage tank 310 through the circulation pump, and by repeating the above processes, continuous circulation of the heat transfer medium can be realized.
As shown in fig. 1, the top of the reforming chamber 120 is further provided with a filling port 124, and the filling port 124 is used for filling or replacing the heat transfer medium. By providing the filling port 124, it is convenient to fill the thermally conductive medium into the reforming chamber 120 when it is first used. In addition, the heat conducting medium is convenient to pour out and replace after long-time use, and the use of the deteriorated heat conducting medium is avoided. In practical application, the heat conducting medium can be replaced once before and after each working period, so that the operation of the device is not influenced.
Further, a thermocouple 500 is provided at the top of the reforming chamber 120. By providing the thermocouple 500, it is convenient to measure the temperature in the reforming chamber 120, thereby conveniently observing the entire reforming reaction process.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises an element.
In this specification, each embodiment is described in a related manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments. In particular, for system embodiments, since they are substantially similar to method embodiments, the description is relatively simple, as relevant to see a section of the description of method embodiments.
The foregoing is merely a preferred embodiment of the present application, and is not intended to limit the scope of the present application. Any modifications, equivalent substitutions, improvements, etc. that are within the spirit and principles of the present application are intended to be included within the scope of the present application.

Claims (10)

1. A methanol-to-water reforming hydrogen production apparatus, comprising:
the box body (100) is provided with a base (110), the interior of the box body (100) is divided into a reforming chamber (120) and a heating chamber (130), and the reforming chamber (120) is a closed cavity;
a reforming reactor (200) positioned in the reforming chamber (120) and comprising a plurality of reaction tubes (211) arranged in an array, wherein the reaction tubes (211) are filled with catalysts; the side wall of the reforming chamber (120) is provided with a raw material inlet (121) and a gas outlet (122), the reforming reactor (200) is respectively communicated with the raw material inlet (121) and the gas outlet (122), the raw material inlet (121) is used for feeding methanol and water into the reforming reactor (200), and the gas outlet (122) is used for feeding gas generated after reforming reaction to flow out, and the gas comprises hydrogen and carbon dioxide;
a heating module (300) comprising a liquid storage tank (310) and a heat conducting medium, wherein the liquid storage tank (310) is positioned in the heating chamber (130) and is used for storing the heat conducting medium; the liquid storage tank (310) is communicated with the reforming chamber (120) so that the heat conducting medium flows into the reforming chamber (120) and is filled between the reaction tubulars (211) and the inner wall of the reforming chamber (120), and the heat conducting medium is used for providing heat for reforming reaction.
2. The methanol-water reforming hydrogen-producing apparatus as defined in claim 1, wherein the reforming reactor (200) comprises a plurality of reaction groups (210) arranged in parallel, each reaction group (210) comprising a plurality of the reaction tubes (211) arranged in series.
3. The methanol-water reforming hydrogen production apparatus as defined in claim 2, wherein the reforming reactor (200) further comprises a total inlet line (213) and a total outlet line (214), the total inlet line (213) being in communication with the feedstock inlet (121), the total outlet line (214) being in communication with the gas outlet (122), each of the reaction groups (210) being in communication with the total inlet line (213) and the total outlet line (214), respectively.
4. A methanol-water reforming hydrogen production apparatus as defined in claim 3, wherein the reaction tubulars (211) comprise a tubular body (2111) and adapters (2112) at both ends of the tubular body (2111), the adapters (2112) being in communication with the main inlet line (213) or the main outlet line (214) or with the adapters (2112) of the adjacent reaction tubulars (211) through pipes.
5. The methanol-water reforming hydrogen generation apparatus as defined in claim 1, wherein the heating module (300) further comprises a burner (320), the burner (320) being disposed below the liquid storage tank (310) and at the base (110); the side wall of the base (110) is provided with a fuel inlet (111), the fuel inlet (111) is communicated with the combustion furnace (320), and the combustion furnace (320) is used for combusting fuel to heat the heat conducting medium in the liquid storage tank (310).
6. The methanol-to-water reforming hydrogen production apparatus of claim 5 wherein the fuel is methanol; an air inlet (131) is formed in the bottom of the side wall of the heating chamber (130), and the air inlet (131) is used for allowing air to enter; an exhaust channel (132) is arranged above the liquid storage tank (310), and the exhaust channel (132) is used for discharging high-temperature gas generated after combustion.
7. The methanol-water reforming hydrogen generator as defined in claim 6, wherein a methanol vaporizer (330) is further provided inside the base (110), the methanol vaporizer (330) is provided with a curved flow passage (331), one end of the curved flow passage (331) is communicated with the fuel inlet (111), and the other end of the curved flow passage (331) is communicated with the combustion furnace (320);
the base (110) is further provided with a heating rod (400), and the heating rod (400) is used for heating the methanol flowing through the curved flow channel (331) so as to enable the methanol to be heated and vaporized.
8. The methanol-water reforming hydrogen generation apparatus as defined in claim 1, wherein the heating module (300) further comprises a circulation pump, the circulation pump being located within the heating chamber (130); one end of the liquid storage tank (310) is communicated with the reforming chamber (120) through the circulating pump, and the other end of the liquid storage tank (310) is communicated with the reforming chamber (120) through a pipeline (340).
9. The methanol-water reforming hydrogen generator of claim 8, wherein the circulation pump is located above the liquid storage tank (310) and communicates with a top end of the liquid storage tank (310), and the circulation pump is used for re-pumping the heat transfer medium flowing through the reforming chamber (120) into the liquid storage tank (310).
10. The methanol-water reforming hydrogen generating apparatus as defined in claim 9, wherein a heat transfer medium outlet (123) is provided at a side wall of the reforming chamber (120), and a heat transfer medium inlet (133) is provided at a side wall of the heating chamber (130); the height of the heat conducting medium outlet (123) is higher than that of the heat conducting medium inlet (133), and the heat conducting medium outlet (123) is communicated with the heat conducting medium inlet (133) through a pipeline arranged outside the box body (100); the inlet end of the circulating pump is communicated with the heat conducting medium inlet (133), and the outlet end of the circulating pump is communicated with the top of the liquid storage tank (310);
the top of the reforming chamber (120) is also provided with a filling port (124), and the filling port (124) is used for filling or replacing the heat-conducting medium; the heat conducting medium is high-temperature heat conducting oil.
CN202311595460.9A 2023-11-27 2023-11-27 Hydrogen production device by methanol-water reforming Pending CN117599691A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311595460.9A CN117599691A (en) 2023-11-27 2023-11-27 Hydrogen production device by methanol-water reforming

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311595460.9A CN117599691A (en) 2023-11-27 2023-11-27 Hydrogen production device by methanol-water reforming

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CN117599691A true CN117599691A (en) 2024-02-27

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