CN114976155A - Hydrogen fuel cell system combining methanol reforming and solid oxide - Google Patents

Hydrogen fuel cell system combining methanol reforming and solid oxide Download PDF

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Publication number
CN114976155A
CN114976155A CN202210470110.9A CN202210470110A CN114976155A CN 114976155 A CN114976155 A CN 114976155A CN 202210470110 A CN202210470110 A CN 202210470110A CN 114976155 A CN114976155 A CN 114976155A
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methanol
solid oxide
hydrogen
fuel cell
reforming
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石嵩
王华峰
尹淑彦
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Shanghai Weijia Tianyi New Energy Technology Co ltd
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Shanghai Weijia Tianyi New Energy Technology Co ltd
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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
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a hydrogen fuel cell system combining methanol reforming and solid oxide, which relates to the technical field of methanol power generation and comprises a methanol reforming hydrogen production system, a hydrogen purification system and a hydrogen fuel cell stack, wherein the hydrogen purification system comprises a solid oxide electrolytic cell and a CO selective oxidation reactor, and the solid oxide electrolytic cell comprises a hydrogen electrode layer, an electrolyte layer and an oxygen electrode layer; the gas outlet of the methanol reforming hydrogen production system is communicated with the gas inlet of the solid oxide electrolytic cell, the gas outlet of the solid oxide electrolytic cell is communicated with the gas inlet of the CO selective oxidation reactor, and the gas outlet of the CO selective oxidation reactor is communicated with the gas inlet of the hydrogen fuel cell stack. The invention uses solid oxide electrolytic cell to electrolyze H 2 O ionization to H 2 And O 2 Generation of O 2 The catalyst is used as oxidizing gas to react with CO, reduces the content of CO, prolongs the service life of a hydrogen fuel cell stack, and does not introduce other redundant gasesAnd also generate H 2 。

Description

Hydrogen fuel cell system combining methanol reforming and solid oxide
Technical Field
The invention relates to the technical field of hydrogen fuel cell stacks, in particular to a hydrogen fuel cell stack system which selectively oxidizes CO without introducing external air.
Background
A fuel cell is a power generation device that directly converts chemical energy contained in chemical substances into electrical energy using an oxidation-reduction reaction. The most widely used of them is H 2 As energy carriersA bulk proton exchange membrane fuel cell.
The proton exchange membrane fuel cell takes a perfluorinated sulfonic acid type ion exchange membrane as an electrolyte, Pt/C as an electrocatalyst, and H 2 Or reforming the gas into fuel, air or O 2 A device for directly converting chemical energy into electric energy as an oxidant. The proton exchange membrane is a perfluorosulfonic acid proton exchange membrane, and the principle is that sulfonic acid groups in the perfluorosulfonic acid membrane are used as proton transfer channels, H 2 Oxidation reaction is carried out on the anode catalyst layer side of the membrane electrode, electrons are lost and become protons, the electrons are transmitted to the cathode catalyst layer side of the membrane electrode through an external circuit, and the protons are transmitted to the cathode catalyst layer through a proton exchange membrane of the membrane electrode. The perfluorosulfonic acid membrane contains a platinum-gold catalyst, the platinum has strong adsorption capacity to CO, and the platinum after CO adsorption can not catalyze H2 into protons and electrons any longer, so that the fuel cell performance is instantly reduced due to the poisoning of the platinum.
In order to ensure the normal operation of the fuel cell, the CO content entering the fuel cell must be strictly controlled, and the hydrogen-rich gas from the reformer can be used for separating H through a palladium membrane separator 2 Purifying to 99.99% concentration, and then entering fuel cell stack to generate hydrogen-oxygen electrochemical reaction.
In summary, CO is a harmful gas for a hydrogen fuel cell stack, and a current general solution is to purify hydrogen after reforming methanol, and then input the purified hydrogen into the fuel cell stack to generate electricity. The metal palladium membrane separator commonly used in the hydrogen purification process is expensive and low in efficiency, so that the industrialization road of the mobile hydrogen production fuel cell system is hindered.
In another solution, the hydrogen purification process is changed into an impurity removal process, and CO is selectively removed by selecting a proper catalyst and reaction temperature to reduce the CO to a proper concentration value, H 2 And CO 2 And other neutral gases. The method reduces the consumption of noble metals, reduces the production cost and breaks the way of hydrogen industrialization.
In the process of selectively removing carbon monoxide, air is introduced to react carbon monoxide with oxygen in the air at a proper temperature under the action of a catalyst to generate carbon dioxide harmless to the fuel cell, so that the purpose of selectively removing carbon monoxide is achieved, however, the introduction of the air brings irrelevant gases such as nitrogen and the like, so that the hydrogen-rich gas is more complex in composition, the concentration of hydrogen in the hydrogen-rich gas is diluted, the reaction efficiency of a subsequent hydrogen fuel cell stack is reduced, and the technical problem is an industrial problem that the development of the methanol reforming hydrogen fuel cell stack is restricted.
Disclosure of Invention
Based on this, it is necessary to address H in the hydrogen-rich gas output from the reformer 2 Purification and reduction of CO content without introducing outside air, and provides a process for selectively removing CO and increasing H content 2 Hydrogen fuel cell systems with combined content of methanol reforming and solid oxide.
The technical scheme of the invention is as follows: a methanol reforming and solid oxide combined hydrogen fuel cell system comprises a methanol reforming hydrogen production system, a hydrogen purification system and a hydrogen fuel cell stack, wherein:
the hydrogen purification system comprises a solid oxide electrolytic cell and a CO selective oxidation reactor, wherein the solid oxide electrolytic cell comprises a hydrogen electrode layer, an electrolyte layer and an oxygen electrode layer, and certain voltage is applied to the solid oxide electrolytic cell so as to enable H flowing through the solid oxide electrolytic cell to flow through the solid oxide electrolytic cell 2 Electrolysis of O to H 2 And O 2 The gas outlet of the methanol reforming hydrogen production system is communicated with the gas inlet of the solid oxide electrolytic cell, the gas outlet of the solid oxide electrolytic cell is communicated with the gas inlet of the CO selective oxidation reactor, the CO selective oxidation reactor is filled with a CO selective oxidation catalyst, and the gas outlet of the CO selective oxidation reactor is communicated with the gas inlet of the hydrogen fuel cell stack.
In one embodiment, the methanol reforming hydrogen production system comprises:
the system comprises a methanol water supply system, a methanol water supply system and a methanol water mixing system, wherein the methanol water supply system comprises a methanol container, a water container and a methanol water mixing container, and the methanol container and the water container are both communicated with an inlet of the methanol water mixing container through pipelines;
the outlet of the methanol-water mixing container is communicated with the inlet of the evaporator through a pipeline, and the evaporator vaporizes the raw material methanol and water;
the outlet of the evaporator is communicated with the inlet of the reformer through a pipeline, a methanol steam reforming catalyst is contained in the reformer, and the reformer is used for reforming raw material methanol and water to produce hydrogen through hydrogen production reaction to generate hydrogen-rich reformed gas.
In one embodiment, a first heat exchanger is arranged between the reformer and the solid oxide electrolysis cell, and a second heat exchanger is arranged between the CO selective oxidation reactor and the hydrogen fuel cell stack.
In one embodiment, the system for reforming methanol to produce hydrogen further comprises a heat supplier, wherein the heat supplier supplies a heat source to the reformer and the evaporator.
In one embodiment, the heater uses methanol as fuel, and the heater is filled with alumina catalyst, and the methanol contacts with the alumina catalyst to generate heat to be used as a heat source.
In one embodiment, the hydrogen purification system further comprises a housing having a receiving space, and the solid oxide electrolysis cell and the CO selective oxidation reactor are integrated in the housing.
In one embodiment, the methanol water supply system inputs water/methanol mixture molar ratio in the evaporator to be 1.0-2.5.
Compared with the related art, the hydrogen fuel cell system combining methanol reforming and solid oxide provided by the invention has the following beneficial effects:
1. the methanol reforming hydrogen production system of the invention carries out reforming hydrogen production reaction and methanol cracking reaction on methanol and water under high pressure to generate H 2 、CO 2 CO and H 2 O, passing H in the solid oxide electrolytic cell 2 O ionization to H 2 And O 2 Generation of O 2 As the oxidizing gas reacts with CO, the content of CO is greatly reduced, and noble metal catalysts such as Pt and the like and CO are avoidedThe combination of the hydrogen fuel cell and the electrolyte loses activity, thereby prolonging the service life of the hydrogen fuel cell stack,
2. the invention is different from other schemes of introducing air as an oxidant to react with CO, and other redundant gases such as N in the air are not introduced 2 And also electrolyze to produce H 2 So that the system H 2 The concentration is increased, and more H is provided for the fuel cell 2 And (3) fuel.
3. The invention integrates the solid oxide electrolytic cell and the CO selective oxidation reactor in the same shell to form a hydrogen purification system, and has the advantages of simple structure, low production cost and high CO catalysis efficiency.
Drawings
FIG. 1 is a block diagram of a methanol reforming and solid oxide combined hydrogen fuel cell system;
FIG. 2 is a block diagram of a methanol reforming hydrogen production system;
figure 3 is a schematic of a solid oxide electrolytic cell.
Reference numerals: 1. a methanol reforming hydrogen production system; 11. a methanol water supply system; 111. a methanol container; 112. a water container; 113. a methanol-water mixing container; 114. an MCU controller; 115. a methanol metering pump; 116. a water metering pump; 117. a methanol-water mixing metering pump; 12. an evaporator; 13. a reformer; 14. a heat supply device; 2. a hydrogen purification system; 21. a solid oxide electrolytic cell; 211. a hydrogen electrode layer; 212. an electrolyte layer; 213. an oxygen electrode layer; 22. a CO selective oxidation reactor; 23. a housing; 3. a hydrogen fuel cell stack; 4. a first heat exchanger; 5. and a second heat exchanger.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows: as shown in figures 1 to 3, the invention provides a nailThe hydrogen fuel cell system combining alcohol reforming and solid oxide comprises a methanol reforming hydrogen production system 1, a hydrogen purification system 2 and a hydrogen fuel cell stack 3, wherein the methanol reforming hydrogen production system 1 carries out reforming hydrogen production reaction and methanol cracking reaction on methanol and water at 200-350 ℃ and normal pressure (0.2-0.5bar) to generate H 2 、CO 2 CO and H 2 The CO content of the O-rich reformed gas is generally lower than 5 percent, and then the O-rich reformed gas is conveyed to a hydrogen purification system 2, and the system is used for reducing the CO concentration in the O-rich reformed gas and simultaneously increasing the H 2 Then the system will enrich the H 2 As stack anode reactant gas into the hydrogen fuel cell stack 3, H 2 Oxidation reaction occurs in the hydrogen fuel cell stack 3 to convert H 2 The chemical energy contained in the solution is converted into electric energy.
Wherein, the gas outlet of the methanol reforming hydrogen production system 1 is communicated with the gas inlet of the solid oxide electrolytic cell 21, the hydrogen purification system 2 comprises the solid oxide electrolytic cell 21 and the CO selective oxidation reactor 22, the solid oxide electrolytic cell 21 comprises a hydrogen electrode layer 211, an electrolyte layer 212 and an oxygen electrode layer 213, the electrolyte layer 212 is positioned between the hydrogen electrode layer 211 and the oxygen electrode layer 213, and a certain voltage is applied to the solid oxide electrolytic cell 21 to enable part of H flowing through the interior of the solid oxide electrolytic cell 21 to flow through 2 Electrolysis of O to H 2 And O 2- ，O 2- The ions permeate the electrolyte layer 212 to release electrons in the oxygen electrode layer to form O 2 The solid oxide electrolytic cell 21 has O 2 Gas outlet, H 2 The two gas outlets are communicated with the gas inlet of the CO selective oxidation reactor 22, a CO selective oxidation catalyst is filled in the CO selective oxidation reactor 22, the gas outlet of the CO selective oxidation reactor 22 is communicated with the gas inlet of the hydrogen fuel cell stack 3, and the CO selective oxidation catalyst is used for catalyzing CO and O 2 Reaction of CO to CO 2 The concentration of CO in the hydrogen-rich gas is reduced to be lower than 0.2ppm, so that the hydrogen-rich gas can enter the hydrogen fuel cell stack 3, and the performance of the hydrogen fuel cell stack 3 is not reduced.
In the present embodiment, the material of the hydrogen electrode layer 211 is selected to be nickel-yttria-stabilizedThe oxygen electrode layer 213 is made of lanthanum strontium cobalt iron, the electrolyte layer 212 is made of yttria stabilized zirconia, and the hydrogen electrode layer 211 is a porous ceramic structure capable of conducting electrons to generate H 2 (ii) a The electrolyte layer 212 is a dense perovskite ceramic that conducts O 2- (ii) a The oxygen electrode layer 213 is a porous ceramic structure capable of conducting O 2- Transporting air and generated O 2 。
In other embodiments, the electrolyte layer 212 includes, but is not limited to, fluorite structured oxides, such as zirconia (ZrO), and perovskite structured oxides 2 ) Cerium oxide (CeO) 2 ) And bismuth oxide (Bi) 2 O 3 ) (ii) a Oxides of perovskite structure, e.g. LaGaO 3 Based on a solid oxide.
When a voltage is applied to the solid oxide electrolytic cell 21, H at the hydrogen electrode layer 211 is generated by electromotive force 2 Decomposition of O to H under catalysis of Ni 2 And O 2- The reaction equation is H 2 O+2e - →H 2 +O 2- O produced 2- After passing through the electrolyte layer 212 to the oxygen electrode layer 213, the electron generation O is lost by the catalyst 2 The reaction equation is O 2- →2e - +1/2O 2 。
Further, the system for producing hydrogen by reforming methanol 1 comprises a methanol-water supply system 11, an evaporator 12 and a reformer 13 connected in this order, the methanol-water supply system 11 comprises a methanol container 111, the methanol reforming device comprises a water container 112 and a methanol-water mixing container 113, wherein the methanol container 111 is used for storing methanol, the water container 112 is used for storing water, the methanol-water mixing container 113 is used for storing a methanol aqueous solution, the methanol container 111 and the water container 112 are both communicated with an inlet of the methanol-water mixing container 113 through pipelines, an outlet of the methanol-water mixing container 113 is communicated with an inlet of an evaporator 12 through a pipeline, the evaporator 12 vaporizes raw material methanol and water to produce gaseous methanol water, an outlet of the evaporator 12 is communicated with an inlet of a reformer 13 through a pipeline, the reformer 13 contains a methanol-water reforming catalyst, and the reformer 13 is used for reforming the raw material methanol and the water to produce hydrogen and react to produce reformed synthetic gas.
In this embodimentIn the method, the molar ratio of water and methanol input into the methanol-water mixing container 113 from the methanol container 111 and the water container 112 is 1.0-2.5, but not limited thereto, and the molar ratio of water and methanol may be adjusted according to the work efficiency of the methanol reforming hydrogen production system 1 and the hydrogen purification system 2 in actual work, but it should be noted that the input of water is necessarily greater than that of methanol, so that water cannot be completely consumed after the methanol and water undergo the reforming hydrogen production reaction and the methanol cracking reaction, and a part of the remaining H is not completely consumed 2 O can react with CO in the reformer 13 to reduce the CO concentration, and heat can be supplied to the inside of the reformer 13 since the CO oxidation process is an exothermic process, and another part of the remaining H 2 O is fed to a solid oxide electrolysis cell 21, which can feed H 2 O ionization to H 2 And O 2 Generation of O 2 As an oxidising gas with CO to CO 2 Thus greatly reducing the content of CO, avoiding the combination of noble metal catalysts such as Pt and the like and CO, thereby prolonging the service life of the hydrogen fuel cell stack 3, and introducing other redundant gases such as N in the air with the existing technical means of introducing the air as an oxidant to react with the CO without introducing other redundant gases 2 And also electrolyze to produce H 2 So that the system H 2 The concentration is increased to provide more H for the hydrogen fuel cell stack 3 2 And (3) fuel.
In order to further optimize the above embodiment, since the reaction temperatures of the reformer 13, the solid oxide electrolysis cell 21, the CO selective oxidation reactor 22 and the hydrogen fuel cell stack 3 are different, the first heat exchanger 4 is provided between the reformer 13 and the solid oxide electrolysis cell 21, the second heat exchanger 5 is provided between the CO selective oxidation reactor 22 and the hydrogen fuel cell stack 3, and the temperature is adjusted by the first heat exchanger 4 and the second heat exchanger 5.
In addition, the system 1 for producing hydrogen by reforming methanol further comprises a heat supplier 14, wherein the heat supplier 14 supplies heat sources to the reformer 13 and the evaporator 12, and unreacted hydrogen in the hydrogen fuel cell stack 3 enters the oxidation chamber of the reformer 13 again for oxidation reaction so as to provide heat required by the reforming reaction of methanol.
Further, the heater 14 uses methanol as fuel, and methanol and H are input 2 Etc. haveMaterial of calorific value and O in air 2 An oxidizing agent is filled in the heater 14, the methanol contacts the alumina catalyst and then generates heat to become a heat source, and the heater 14 transmits the generated heat source to the reformer 13 and the evaporator 12; according to actual needs, an electric heating device can be arranged in the reformer 13, and a SiC heating plate can be used as the electric heating device.
In addition, the hydrogen purification system 2 further comprises a housing 23 having a receiving space, the solid oxide electrolysis cell 21 and the CO selective oxidation reactor 22 are integrated in the housing 23, and the gas generated by the solid oxide electrolysis cell 21 is directly discharged into the CO selective oxidation reactor 22, so that the structure is simple, the production cost is low, and the CO catalytic efficiency is high.
The CO selective oxidation catalyst is preferably patentee: the patent number 201911182018.7 of the institute of chemical and physical university of Chinese academy of sciences, prepared under the condition of rich hydrogen in carbon monoxide preferentially oxidizes the catalyst, and the hydrogen fuel cell stack 3 is one of a proton exchange membrane hydrogen fuel cell stack, a hydrogen phosphate fuel cell stack, a molten carbonate hydrogen fuel cell stack or a solid oxide hydrogen fuel cell stack.
The reformer 13, the evaporator 12, the first heat exchanger 4 and the second heat exchanger 5 all adopt high-temperature gas or heat conducting oil as heat exchange media.
Further, the current reformer 13 for methanol mainly comprises a fixed bed reactor, a packed bed reactor, a membrane reactor and a microchannel reactor, and the microchannel reactor has the advantages of small volume, high safety, high heat and mass transfer efficiency, quick start-up, good vibration resistance and the like. The catalyst mainly comprises a non-noble metal catalyst and a noble metal catalyst at present, and the catalyst has the advantages of good stability, difficult poisoning, high activity, good selectivity, less attenuation of long-term working performance and the like, so that the methanol steam reforming catalyst coated on the surface of the reformer 13 In the application is the noble metal catalyst Pt/In 2 O 3 /Al 2 O 3 Catalyst Pt/In 2 O 3 /Al 2 O 3 The optimum reforming temperature of (2) is 350 c, so that the evaporator 12 vaporizes and heats the original methanol-water to a temperature required for the methanol reforming reaction.
It should be noted that the hydrogen fuel cell stack 3 is divided into a low temperature stack and a high temperature stack, the operating temperature of the low temperature stack is lower than 100 ℃, a perfluorosulfonic acid membrane is typically used as a proton permeable membrane, and due to the special characteristics of the perfluorosulfonic acid membrane, a hydrothermal management system must be considered in the design process, so that the hydrogen gas has high purity requirement and is very sensitive to CO. On the contrary, the high temperature galvanic pile reaction temperature exceeds 100 ℃, has the advantages of fast chemical reaction rate, high CO tolerance, simple water heat management and the like, is more suitable for being coupled with a reformer as a power generation device, the hydrogen fuel cell galvanic pile 3 of the application can adopt the high temperature galvanic pile, hydrogen-rich reformed gas is arranged at the inlet of the anode of the high temperature galvanic pile, low hydrogen reformed gas is arranged at the outlet of the anode, and O conveyed by the solid oxide electrolytic cell 21 is arranged at the inlet of the cathode 2 And hypoxic air is at the cathode outlet.
Example two: as shown in fig. 2, the methanol reforming hydrogen production system 1 further includes a methanol-water output control system, the methanol-water output control system includes an MCU (Micro Controller Unit) Controller 114, a methanol metering pump 115, a water metering pump 116 and a methanol-water mixing metering pump 117, the MCU Controller 114 is in control signal connection with the methanol metering pump 115, the water metering pump 116 and the methanol-water mixing metering pump 117, the methanol metering pump 115 is connected with the methanol container 111, the water metering pump 116 is connected with the water container 112, the methanol-water mixing metering pump 117 and the methanol-water mixing container 113, liquid level meters are disposed in the methanol container 111, the water container 112 and the methanol-water mixing container 113, so that the methanol container 111, the water container 112 and the methanol-water mixing container 113 can send liquid level signals to the MCU Controller 114, the MCU Controller 114 can send driving signals to the methanol 115, the water metering pump 116 and the methanol-water mixing metering pump 117, thus, the output of methanol and water can be accurately regulated.
Example three:
the invention provides a hydrogen production and power generation method of a hydrogen fuel cell system combining methanol reforming and solid oxide, which comprises the following steps:
(1) the molar ratio of methanol to water is 1.0-2.5, the water inflow is larger than that of methanol, the methanol and the water are vaporized by an evaporator 12 and enter a reformer 13 to carry out reforming hydrogen production reaction and methanol cracking reaction at 300 ℃ and 1-5Mpa to generate H-rich gas 2 、CO 2 CO and H 2 A hydrogen-rich reformed gas of O;
(2) the hydrogen-rich reformed gas is fed into a solid oxide electrolytic cell 21 and a CO selective oxidation reactor 22, and H is electrolyzed in the solid oxide electrolytic cell 21 2 Generating O by the electrolytic reaction of O 2 And H 2 ；
(3) The solid oxide electrolytic cell 21 feeds the hydrogen-rich reformed gas into a CO selective oxidation reactor 22, and O is introduced into the CO selective oxidation reactor 22 2 Preferentially react with CO to generate CO under the action of CO selective oxidation catalyst 2 Reducing the concentration of CO to less than 0.2 ppm;
(4) the CO selective oxidation reactor 22 feeds the hydrogen-rich reformed gas to the hydrogen fuel cell stack 3, and the H in the hydrogen-rich reformed gas 2 Oxidation reaction takes place to remove H 2 The chemical energy contained in the solution is converted into electric energy.
The above examples only show several embodiments of the present invention, and the description thereof is specific and detailed, but not to be construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (7)

1. The utility model provides a hydrogen fuel cell system that methanol reforming and solid oxide combine, includes methanol reforming hydrogen manufacturing system (1), hydrogen clean system (2) and hydrogen fuel cell pile (3), its characterized in that:
the hydrogen purification system (2) comprises a solid oxide electrolytic cell (21) and a CO selective oxidation reactor (22), wherein the solid oxide electrolytic cell (21) comprises a hydrogen electrode layer (211), an electrolyteA layer (212) and an oxygen electrode layer (213) to which a voltage is applied to the solid oxide electrolytic cell (21) to flow H inside thereof 2 Electrolysis of O to H 2 And O 2 ；
The gas outlet of the methanol reforming hydrogen production system (1) is communicated with the gas inlet of the solid oxide electrolytic cell (21), the gas outlet of the solid oxide electrolytic cell (21) is communicated with the gas inlet of the CO selective oxidation reactor (22), the CO selective oxidation reactor (22) is filled with a CO selective oxidation catalyst, and the gas outlet of the CO selective oxidation reactor (22) is communicated with the gas inlet of the hydrogen fuel cell stack (3).
2. The methanol reforming and solid oxide combined hydrogen fuel cell system according to claim 1, wherein the methanol reforming hydrogen production system (1) comprises:
the methanol water supply system (11) comprises a methanol container (111), a water container (112) and a methanol water mixing container (113), wherein the methanol container (111) and the water container (112) are communicated with an inlet of the methanol water mixing container (113) through pipelines;
the outlet of the methanol-water mixing container (113) is communicated with the inlet of the evaporator (12) through a pipeline, and the evaporator (12) vaporizes the raw material methanol and water;
and the outlet of the evaporator (12) is communicated with the inlet of the reformer (13) through a pipeline, a methanol steam reforming catalyst is contained in the reformer (13), and the reformer (13) is used for reforming raw material methanol and water to produce hydrogen-rich reformed gas.
3. A methanol reforming and solid oxide combined hydrogen fuel cell system according to claim 2, characterized in that a first heat exchanger (4) is provided between the reformer (13) and the solid oxide electrolysis cell (21), and a second heat exchanger (5) is provided between the CO selective oxidation reactor (22) and the hydrogen fuel cell stack (3).
4. The methanol reforming and solid oxide combined hydrogen fuel cell system according to claim 2, wherein the methanol reforming hydrogen production system (1) further comprises a heat supplier (14), and the heat supplier (14) supplies a heat source into the reformer (13) and the evaporator (12).
5. The methanol reforming and solid oxide combined hydrogen fuel cell system according to claim 4, wherein the heater (14) uses methanol as fuel, and the heater (14) is filled with an alumina catalyst, and methanol contacts with the alumina catalyst to generate heat as a heat source.
6. A methanol reforming and solid oxide combined hydrogen fuel cell system according to claim 1, characterized in that the hydrogen purification system (2) further comprises a housing (23) with a receiving space, the solid oxide electrolysis cell (21) and the CO selective oxidation reactor (22) being integrated in the housing (23).
7. The methanol reforming and solid oxide combined hydrogen fuel cell system according to claim 2, wherein the methanol water supply system (11) has a water/methanol mixing molar ratio of 1.0 to 2.5 as input to the evaporator (12).
CN202210470110.9A 2022-04-28 2022-04-28 Hydrogen fuel cell system combining methanol reforming and solid oxide Pending CN114976155A (en)

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