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

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

A hydrogen fuel cell system combining methanol reforming and solid oxide

technical field

The present invention relates to the technical field of hydrogen fuel cell stacks, in particular to a hydrogen fuel cell stack system for selectively oxidizing CO without introducing external air.

Background technique

A fuel cell is a power generation device that directly converts chemical energy contained in chemical substances into electrical energy using a redox reaction. Among them, the most widely used is the proton exchange membrane fuel cell with _H2 as the energy carrier.

Proton exchange membrane fuel cells use perfluorosulfonic acid ion exchange membrane as electrolyte, Pt/C as electrocatalyst, _H2 or reformed gas as fuel, air or _O2 as oxidant, and directly convert chemical energy into electrical energy. device. The proton exchange membrane used is generally a perfluorosulfonic acid proton exchange membrane. The principle is that the sulfonic acid group in the perfluorosulfonic acid membrane acts as a proton transfer channel, and H ₂ undergoes an oxidation reaction on the anode catalytic layer side of the membrane electrode and loses it. The electrons become protons, and the electrons are transferred to the cathode catalytic layer side of the membrane electrode through the external circuit, and the protons are transferred to the cathode catalytic layer through the proton exchange membrane of the membrane electrode. The perfluorosulfonic acid membrane contains platinum catalyst. Platinum has a strong adsorption capacity for CO. After CO adsorption, platinum can no longer catalyze H2 into protons and electrons.

In order to make the fuel cell work normally, the CO content entering the fuel cell must be strictly controlled. The hydrogen _- rich gas from the reformer can be purified to a concentration of 99.99% by passing through a palladium membrane separator, and then entering the fuel cell stack to generate hydrogen. Oxygen electrochemical reaction.

To sum up, CO is a harmful gas for hydrogen fuel cell stacks. The current general solution is to purify hydrogen after methanol reformation, and the purified hydrogen is then fed into the fuel cell stack to generate electricity. The metal palladium membrane separator commonly used in the hydrogen purification process is expensive and inefficient, which hinders the industrialization of the mobile hydrogen production fuel cell system.

Another solution is to turn the hydrogen purification process into a decontamination process, and select a suitable catalyst and reaction temperature to selectively remove CO and reduce it to a suitable concentration value, while other neutral gases such as _H2 and _CO2 are retained. This method reduces the amount of precious metals, reduces production costs, and makes the road to hydrogen industrialization suddenly clear.

In the process of selectively removing carbon monoxide, the usual method is to introduce air, and under the action of a suitable temperature and catalyst, carbon monoxide and oxygen in the air react to generate carbon dioxide that is harmless to the fuel cell, so as to achieve the selective removal of carbon monoxide. However, the introduction of air brings irrelevant gases such as nitrogen, which makes the composition of the hydrogen-rich gas more complex, dilutes the concentration of hydrogen in the hydrogen-rich gas, and reduces the reaction efficiency of the subsequent hydrogen fuel cell stack. This technical problem It is an industry problem restricting the development of methanol reforming hydrogen fuel cell stacks.

SUMMARY OF THE INVENTION

Based on this, it is necessary to provide a methanol heavy _- duty methanol that can selectively remove _CO and increase H integrated and solid oxide combined hydrogen fuel cell system.

The technical scheme of the present invention is: a hydrogen fuel cell system combining methanol reforming and solid oxide, including a methanol reforming hydrogen production system, a hydrogen purification system and a hydrogen fuel cell stack, wherein:

The hydrogen purification system includes a solid oxide electrolytic cell and a CO selective oxidation reactor, the solid oxide electrolytic cell includes a hydrogen electrode layer, an electrolyte layer and an oxygen electrode layer, and a certain voltage is applied to the solid oxide electrolytic cell, To electrolyze the H ₂ O flowing through it to generate 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, and the solid oxide electrolytic cell The gas outlet of the CO selective oxidation reactor is connected 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 connected to the hydrogen selective oxidation reactor. The air inlet of the fuel cell stack is communicated.

In one embodiment, the methanol reforming hydrogen production system includes:

a methanol water supply system, 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 all communicated with the inlet of the methanol water mixing container through a pipeline;

an evaporator, the outlet of the methanol-water mixing container is communicated with the inlet of the evaporator through a pipeline, and the evaporator vaporizes raw methanol and water;

A reformer, the outlet of the evaporator is communicated with the inlet of the reformer through a pipeline, the reformer contains a methanol steam reforming catalyst, and the reformer is used for reforming raw methanol and water The hydrogen production reaction produces hydrogen-rich reformed gas.

In one embodiment, a heat exchanger is provided between the reformer and the solid oxide electrolysis cell, and a heat exchanger is provided between the CO selective oxidation reactor and the hydrogen fuel cell stack Device two.

In one of the embodiments, the methanol reforming hydrogen production system further includes a heater, and the heater supplies a heat source to the reformer and the evaporator.

In one embodiment, the heater uses methanol as a fuel, and the heater is filled with an alumina catalyst, and the methanol and the alumina catalyst generate heat in contact with each other and become a heat source.

In one of the embodiments, the hydrogen purification system further includes a housing with an accommodating space, and the solid oxide electrolysis cell and the CO selective oxidation reactor are both integrated in the housing.

In one embodiment, the mixed molar ratio of water/methanol input into the evaporator by the methanol water supply system is 1.0-2.5.

Compared with the related art, the hydrogen fuel cell system of methanol reforming and solid oxide combination provided by the present invention has the following beneficial effects:

1. The methanol reforming hydrogen production system of the present invention performs 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. Among them, H ₂ O is ionized to generate H ₂ and O ₂ , and the generated O ₂ acts as an oxidizing gas to react with CO, which greatly reduces the content of CO, avoids the combination of noble metal catalysts such as Pt and CO, and loses its activity. Thereby increasing the life of the hydrogen fuel cell stack,

2. The present invention is different from other schemes that introduce air as an oxidant to react with CO, and does not introduce other excess gases, such as N ₂ in the air, and also generates H ₂ by electrolysis, which increases the concentration of H ₂ in the system and provides more fuel cells. more _H2 fuel.

3. The present invention integrates the solid oxide electrolytic cell and the CO selective oxidation reactor in the same shell to form a hydrogen purification system, with simple structure, low production cost and high CO catalytic efficiency.

Description of drawings

1 is a block diagram of a hydrogen fuel cell system incorporating methanol reforming and solid oxide;

Fig. 2 is the block diagram of methanol reforming hydrogen production system;

Figure 3 is a schematic diagram of a solid oxide electrolysis cell.

Reference numerals: 1, methanol reforming hydrogen production system; 11, methanol water supply system; 111, methanol container; 112, water container; 113, methanol water mixing container; 114, MCU controller; 115, methanol metering pump; 116 , water metering pump; 117, methanol-water mixing metering pump; 12, evaporator; 13, reformer; 14, heater; 2, hydrogen purification system; 21, solid oxide electrolytic cell; 211, hydrogen electrode layer; 212, electrolyte layer; 213, oxygen electrode layer; 22, CO selective oxidation reactor; 23, shell; 3, hydrogen fuel cell stack; 4, heat exchanger one; 5, heat exchanger two.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments; based on the The embodiments of the present invention, and all other embodiments obtained by those of ordinary skill in the art without creative work, fall within the protection scope of the present invention.

Embodiment 1: As shown in Figures 1 to 3, the present invention provides a methanol reforming and solid oxide combined hydrogen fuel cell system, including a methanol reforming hydrogen production system 1, a hydrogen purification system 2 and a hydrogen fuel cell Power stack 3, methanol reforming hydrogen production system 1 The methanol and water undergo reforming hydrogen production reaction and methanol cracking reaction at 200 ~ 350 ℃ and normal pressure (0.2-0.5 bar) to generate H ₂ , CO ₂ , CO The hydrogen-rich reformed gas with H ₂ O, the by-product CO content is generally less than 5%, and then the hydrogen-rich reformed gas is transported to the hydrogen purification system 2, and the system is used to reduce the CO concentration in the hydrogen-rich reformed gas, and at the same time Increase the concentration of H ₂ , and then the system uses the enriched H ₂ as the stack anode reaction gas to enter the hydrogen fuel cell stack 3, and the H ₂ undergoes an oxidation reaction in the hydrogen fuel cell stack 3 stack, and the H ₂ is in The contained chemical energy is converted into electrical energy.

Wherein, the outlet of the methanol reforming hydrogen production system 1 is communicated with the inlet of the solid oxide electrolytic cell 21, and the hydrogen purification system 2 includes a solid oxide electrolytic cell 21 and a CO selective oxidation reactor 22. The solid oxide electrolytic cell 21 includes a hydrogen electrode layer 211, an electrolyte layer 212 and an oxygen electrode layer 213. The electrolyte layer 212 is located between the hydrogen electrode layer 211 and the oxygen electrode layer 213. Part of H ₂ O is electrolyzed to generate H ₂ and O ^2- , O ^2- ions permeate through the electrolyte layer 212 and release electrons at the oxygen electrode layer to form O ₂ , the solid oxide electrolytic cell 21 has an O ₂ outlet, H ₂ and mixed The gas outlet, the two gas outlets are connected with the 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 connected to the CO selective oxidation reactor 22. The air inlet of the hydrogen fuel cell stack 3 is connected, and the CO selective oxidation catalyst is used to catalyze the reaction of CO and O ₂ , so that CO is converted into CO ₂ , and the concentration of CO in the hydrogen-rich gas is reduced, so that the concentration is lower than 0.2ppm, The hydrogen-rich gas can enter the hydrogen fuel cell stack 3 , and the performance of the hydrogen fuel cell stack 3 will not be degraded.

In this embodiment, the material of the hydrogen electrode layer 211 is selected as nickel-yttria stabilized zirconia, the material of the oxygen electrode layer 213 is selected as lanthanum strontium cobalt iron, the electrolyte layer 212 is selected as yttria stabilized zirconia, and the hydrogen electrode layer 211 It is a porous ceramic structure, which can conduct electrons to generate H ₂ ; the electrolyte layer 212 is a dense perovskite ceramic, which can conduct O ^2- ; the oxygen electrode layer 213 is a porous ceramic structure, which can conduct O ^2- , Transport air and generated O ₂ .

In other embodiments, the electrolyte layer 212 includes, but is not limited to, fluorite-structured oxides and perovskite-structured oxides, fluorite-structured oxides such as zirconia (ZrO ₂ ), ceria (CeO ₂ ), and bismuth oxide ( Bi ₂ O ₃ ); oxides of perovskite structure such as LaGaO ₃ based solid oxides.

When a voltage is applied to the solid oxide electrolytic cell 21, under the action of electromotive force, the H ₂ O at the hydrogen electrode layer 211 is decomposed into H ₂ and O ^2- under the catalysis of Ni ^, and the reaction equation is H ₂ O+2e- →H ₂ +O ^2- , after the generated O ^2- passes through the electrolyte layer 212 and reaches the oxygen electrode layer 213, it loses electrons under the action of the catalyst to generate O ₂ , the reaction equation is O ^2- →2e ^- +1/2O ₂ .

In addition, the methanol reforming hydrogen production system 1 includes a methanol water supply system 11, an evaporator 12 and a reformer 13 connected in sequence, and the methanol water supply system 11 includes a methanol container 111, a water container 112 and a methanol water mixing container 113. Methanol The container 111 is used to store methanol, the water container 112 is used to store water, and the methanol-water mixing container 113 is used to store methanol aqueous solution. The outlet of the mixing vessel 113 is communicated with the inlet of the evaporator 12 through a pipeline. The evaporator 12 vaporizes the raw methanol and water to produce gaseous methanol water. The outlet of the evaporator 12 is communicated with the inlet of the reformer 13 through a pipeline, and the The reformer 13 contains a methanol steam reforming catalyst, and the reformer 13 is used for reforming the raw methanol and water to produce hydrogen by reforming the reaction gas.

In this embodiment, the molar ratio of water and methanol input from the methanol container 111 and the water container 112 to the methanol-water mixing container 113 is 1.0-2.5, but it is not limited to this. 1 and the working efficiency of the hydrogen purification system 2 to adjust the molar ratio of water and methanol, but it should be noted that the input amount of water must be greater than that of methanol, so that methanol and water will undergo reforming hydrogen production reaction and methanol cracking reaction. After the oxidation process, the water cannot be completely consumed, and a part of the remaining H ₂ O can react with CO in the reformer 13 to reduce the concentration of CO. Since the process of CO oxidation is an exothermic process, it can be supplied to the reformer 13 . heat, and another part of the remaining H ₂ O is sent to the solid oxide electrolytic cell 21, which can ionize H ₂ O to generate H ₂ and O ₂ , and the generated O ₂ acts as an oxidizing gas and reacts with CO to generate CO ₂ , so that That is, the content of CO is greatly reduced, and the combination of noble metal catalysts such as Pt and CO is avoided, thereby improving the life of the hydrogen fuel cell stack 3. Compared with the existing technical means of introducing air as an oxidant to react with CO, no other technology is introduced. The excess gas, such as N ₂ in the air, also electrolyzes to produce H ₂ , which increases the H ₂ concentration in the system and provides more H ₂ fuel for the hydrogen fuel cell stack 3 .

The above embodiment is further optimized. Since the reaction temperatures of the reformer 13, the solid oxide electrolytic cell 21, the CO selective oxidation reactor 22 and the hydrogen fuel cell stack 3 are different, the reformer 13 and the solid oxide electrolytic cell have different reaction temperatures. A heat exchanger 1 4 is arranged between 21 , a heat exchanger 2 5 is arranged between the CO selective oxidation reactor 22 and the hydrogen fuel cell stack 3 , and the temperature is adjusted by the heat exchanger 1 4 and the heat exchanger 2 5 .

In addition, the methanol reforming hydrogen production system 1 further includes a heater 14, and the heater 14 supplies the heat source to the reformer 13 and the evaporator 12, and the unreacted hydrogen in the hydrogen fuel cell stack 3 enters the reformer again The oxidation chamber of the vessel 13 conducts the oxidation reaction to provide the heat required for the methanol reforming reaction.

Further, the heater 14 uses methanol as fuel, and inputs substances with calorific value such as methanol, _H2 , and oxidants such as _O2 in the air, and the heater 14 is filled with an alumina catalyst. After methanol contacts the alumina catalyst The heat generated becomes 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 installed in the reformer 13, and the electric heating device can use a SiC heating sheet.

In addition, the hydrogen purification system 2 further includes a casing 23 with an accommodating space, the solid oxide electrolytic cell 21 and the CO selective oxidation reactor 22 are integrated in the casing 23, and the gas generated by the solid oxide electrolytic cell 21 is directly discharged to the In the CO selective oxidation reactor 22, the structure is simple, the production cost is low, and the CO catalytic efficiency is high.

The CO selective oxidation catalyst is preferably used by the patentee: Dalian Institute of Chemical Physics, Chinese Academy of Sciences, with the patent number of 201911182018.7, the prepared catalyst for preferential oxidation of carbon monoxide and hydrogen-rich conditions, and the hydrogen fuel cell stack 3 is a proton exchange membrane hydrogen fuel cell stack , hydrogen phosphate fuel cell stack, molten carbonate hydrogen fuel cell stack or solid oxide hydrogen fuel cell stack.

The reformer 13, the evaporator 12, the heat exchanger one 4 and the heat exchanger two 5 all use high temperature gas or heat transfer oil as the heat exchange medium.

Further, at present, the methanol reformer 13 mainly includes a fixed bed reactor, a packed bed reactor, a membrane reactor and a microchannel reactor. Because the microchannel reactor has the advantages of small volume, high safety, high heat and mass transfer efficiency, The reformer 13 in this application adopts a micro-channel reactor to couple the reforming chamber and the oxidation chamber together, and the two sides of the micro-channel are the reforming side and the oxidation side respectively. At present, the catalysts used for hydrogen production from methanol reforming mainly include non-precious metal catalysts and precious metal catalysts. Because pin-based catalysts have many advantages, such as good stability, not easy to be poisoned, high activity, good selectivity, and less attenuation of long-term working performance. The methanol steam reforming catalyst coated on the surface of the reformer 13 in the application is a precious metal catalyst Pt/In ₂ O ₃ /Al ₂ O ₃ , and the optimum reforming temperature of the catalyst Pt/In ₂ O ₃ /Al ₂ O ₃ is Therefore, the evaporator 12 vaporizes the original methanol water and heats it to the 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 working temperature of the low temperature stack is lower than 100 ° C, and a perfluorosulfonic acid membrane is typically used as the proton permeation membrane. Due to the special characteristics of the membrane, the hydrothermal management system must be considered in the design process, which requires high purity of hydrogen and is very sensitive to CO. On the contrary, the high temperature stack has the advantages of fast chemical reaction rate, high CO tolerance, simple hydrothermal management, etc., with the reaction temperature exceeding 100 °C, and is more suitable as a power generation device for coupling with a reformer. The hydrogen fuel cell stack of the present application 3. A high temperature stack can be used. The anode inlet of the high temperature stack is hydrogen-rich reformed gas, the anode outlet is low hydrogen reformed gas, the cathode inlet is O ₂ delivered by the solid oxide electrolytic cell 21, and the cathode outlet is Hypoxic air.

Embodiment 2: As shown in FIG. 2, the methanol reforming hydrogen production system 1 further includes a methanol water output control system, and the methanol water output control system includes an MCU (Micro Controller Unit, micro control unit) controller 114, a methanol metering pump 115, The water metering pump 116 and the methanol-water mixing metering pump 117, the MCU controller 114 is connected with the methanol metering pump 115, the water metering pump 116 and the methanol-water mixing metering pump 117 for control signals, and the methanol metering pump 115 is connected with the methanol container 111. The pump 116 is connected to the water container 112, the methanol-water mixing metering pump 117 is connected to the methanol-water mixing container 113, and the methanol container 111, the water container 112 and the methanol-water mixing container 113 are all provided with liquid level gauges, so that the methanol container 111 and the water container 112 are equipped with liquid level gauges. Both the methanol and water mixing container 113 can send liquid level signals to the MCU controller 114, and the MCU controller 114 can send driving signals to the methanol metering pump 115, the water metering pump 116 and the methanol-water mixing metering pump 117, so that the methanol can be accurately adjusted with water output.

Embodiment three:

The present invention provides a hydrogen production and power generation method of a hydrogen fuel cell system combining methanol reforming and solid oxide, comprising the following steps:

(1) The molar ratio of methanol and water is between 1.0 and 2.5, so that the input amount of water is greater than that of methanol. After the methanol and water are vaporized through the evaporator 12, they enter the reformer 13 at 300° C. and 1-5Mpa The reforming hydrogen production reaction and methanol cracking reaction occur under the high pressure of high pressure to generate hydrogen-rich reformed gas rich in H ₂ , CO ₂ , CO and H ₂ O;

(2) the hydrogen-rich reformed gas is input into the solid oxide electrolytic cell 21 and the CO selective oxidation reactor 22, and under the electrolysis of the solid oxide electrolytic cell 21, H ₂ O undergoes an electrolytic reaction to generate O ₂ and H ₂ ;

(3) The solid oxide electrolytic cell 21 feeds the hydrogen-rich reformed gas into the CO selective oxidation reactor 22. In the CO selective oxidation reactor 22, O ₂ preferentially reacts with CO under the action of the CO selective oxidation catalyst to generate CO ₂ , reduce the concentration of CO to less than 0.2ppm;

(4) The CO selective oxidation reactor 22 inputs the hydrogen-rich reformed gas into the hydrogen fuel cell stack 3, and the _H2 in the hydrogen-rich reformed gas undergoes an oxidation reaction, converting the chemical energy contained in the _H2 into electrical energy.

The above embodiments only represent several embodiments of the present invention, and the descriptions thereof are specific and detailed, but should not be construed as a limitation on the scope of the patent of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can also be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (7)

1. A hydrogen fuel cell system combining methanol reforming and solid oxide, comprising a methanol reforming hydrogen production system (1), a hydrogen purification system (2) and a hydrogen fuel cell stack (3), characterized in that: The hydrogen purification system (2) comprises a solid oxide electrolytic cell (21) and a CO selective oxidation reactor (22), the solid oxide electrolytic cell (21) comprises a hydrogen electrode layer (211) and an electrolyte layer (212) ) and an oxygen electrode layer (213), applying a certain voltage to the solid oxide electrolytic cell (21) to electrolyze the H ₂ O flowing through it to generate H ₂ and O ₂ ; The air outlet of the methanol reforming hydrogen production system (1) is communicated with the air inlet of the solid oxide electrolytic cell (21), and the air outlet of the solid oxide electrolytic cell (21) is connected to the CO selective The air inlet of the oxidation reactor (22) is in communication, the CO selective oxidation reactor (22) is filled with a CO selective oxidation catalyst, and the air outlet of the CO selective oxidation reactor (22) is connected to the hydrogen The air inlet of the fuel cell stack (3) is communicated. 2. The hydrogen fuel cell system combining methanol reforming and solid oxide according to claim 1, wherein the methanol reforming hydrogen production system (1) comprises: A methanol water supply system (11), comprising a methanol container (111), a water container (112) and a methanol water mixing container (113), the methanol container (111) and the water container (112) are connected to the methanol container (111) and the water container (112) through pipelines. The inlet of the methanol-water mixing container (113) is communicated; an evaporator (12), 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 raw methanol and water; A reformer (13), the outlet of the evaporator (12) is communicated with the inlet of the reformer (13) through a pipeline, and the reformer (13) contains a methanol steam reforming catalyst, so The reformer (13) is used for reforming the raw methanol and water for hydrogen production to produce hydrogen-rich reformed gas. 3. The hydrogen fuel cell system combining methanol reforming and solid oxide according to claim 2, characterized in that, between the reformer (13) and the solid oxide electrolysis cell (21), a The first heat exchanger (4) is provided with a second heat exchanger (5) between the CO selective oxidation reactor (22) and the hydrogen fuel cell stack (3). 4. The hydrogen fuel cell system combining methanol reforming and solid oxide according to claim 2, wherein the methanol reforming hydrogen production system (1) further comprises a heater (14), the A heater (14) supplies a heat source to the reformer (13) and the evaporator (12). 5. The hydrogen fuel cell system combining methanol reforming and solid oxide according to claim 4, wherein the heater (14) uses methanol as fuel, and the heater (14) The alumina catalyst is filled, and the methanol and the alumina catalyst contact and generate heat to become a heat source. 6 . The hydrogen fuel cell system combining methanol reforming and solid oxide according to claim 1 , wherein the hydrogen purification system ( 2 ) further comprises a casing ( 23 ) having an accommodating space, and the solid Both the oxide electrolysis cell (21) and the CO selective oxidation reactor (22) are integrated in the shell (23). 7 . The hydrogen fuel cell system combining methanol reforming and solid oxide according to claim 2 , wherein the methanol water supply system ( 11 ) inputs the water/methanol mixture in the evaporator ( 12 ). 8 . The molar ratio is 1.0 to 2.5.

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