阅读说明：本技术 一种甲醇水燃料重整制氢系统 (Methanol-water fuel reforming hydrogen production system ) 是由 马友河 王戈 王启浩 孙少东 葛棋 汤伟 严国鑫 樊军 肖延嗣 于 2020-08-04 设计创作，主要内容包括：本发明公开了一种甲醇水燃料重整制氢系统,其包括依次连接的甲醇水燃料进料管、蒸发器、改质器、CO氧化去除装置和富氢混合气体输送管；所述CO氧化去除装置包括LTS催化氧化器和PROX催化氧化器,所述LTS催化氧化器的内部设有铜锌基催化剂,所述PROX催化氧化器的内部设有钌基催化剂。本发明通过LTS催化氧化器和PROX催化氧化器对富氢混合气体进行分阶段氧化处理,逐步降低气体中的CO浓度,保证CO得以被完全去除。本发明系统对甲醇的转化率可达100％,并能完全去除重整混合气体中的CO,系统的启动耗时短,能快速达到重整制氢条件,能耗低,制氢速度快,制氢成本低,具有高效的能量转换效率,环保节能,与燃料电池电堆对接后,发电效率较高。(The invention discloses a methanol-water fuel reforming hydrogen production system, which comprises a methanol-water fuel feeding pipe, an evaporator, a modifier, a CO oxidation removal device and a hydrogen-rich mixed gas conveying pipe which are connected in sequence; the CO oxidation removal device comprises an LTS catalytic oxidation device and a PROX catalytic oxidation device, wherein a copper-zinc-based catalyst is arranged inside the LTS catalytic oxidation device, and a ruthenium-based catalyst is arranged inside the PROX catalytic oxidation device. According to the invention, the LTS catalytic oxidizer and the PROX catalytic oxidizer are used for carrying out staged oxidation treatment on the hydrogen-rich mixed gas, so that the concentration of CO in the gas is gradually reduced, and the CO is ensured to be completely removed. The conversion rate of the system to the methanol can reach 100 percent, the CO in the reformed mixed gas can be completely removed, the starting time of the system is short, the reforming hydrogen production condition can be quickly achieved, the energy consumption is low, the hydrogen production speed is high, the hydrogen production cost is low, the efficient energy conversion efficiency is realized, the environment is protected, the energy is saved, and the power generation efficiency is higher after the system is butted with a fuel cell stack.)

1. A system for reforming methanol-water fuel to produce hydrogen is characterized by comprising a methanol-water fuel feeding pipe, an evaporator, a modifier, a CO oxidation removal device and a hydrogen-rich mixed gas conveying pipe which are sequentially connected; the CO oxidation removal device comprises an LTS catalytic oxidation device and a PROX catalytic oxidation device, wherein a copper-zinc-based catalyst is arranged inside the LTS catalytic oxidation device, and a ruthenium-based catalyst is arranged inside the PROX catalytic oxidation device.

2. The system for hydrogen production by methanol-water fuel reforming according to claim 1, further comprising a burner for heating the reformer, wherein a fuel inlet of the burner is connected to the methanol-water fuel feed pipe; and the other end of the hydrogen-rich mixed gas conveying pipe is respectively connected with an anode gas inlet of the fuel cell and a fuel inlet of the combustor.

3. The system for reforming and producing hydrogen by methanol-water fuel of claim 2, wherein the reformer is cylindrical and is provided with a jacket, a hydrogen production catalyst is filled in the jacket, the jacket is provided with a material inlet and a hydrogen-rich gas outlet, the material inlet is connected with the evaporator, and the hydrogen-rich gas outlet is connected with the air inlet of the LTS catalytic oxidizer.

4. The system for reforming and producing hydrogen by methanol-water fuel according to claim 3, wherein the evaporator comprises a preheater and a heat exchanger, the preheater and the heat exchanger are respectively provided with a liquid passage and a gas passage, an inlet of the liquid passage of the preheater is connected with the methanol-water fuel feeding pipe, an outlet of the liquid passage of the preheater is connected with an inlet of the liquid passage of the heat exchanger, and an outlet of the liquid passage of the heat exchanger is connected with the material inlet of the reformer.

5. The system for reforming methanol-water fuel to produce hydrogen of claim 4, wherein the reformer is further provided with a gas passage for exchanging heat with a jacket thereof; the heat exchanger is arranged in the cylindrical cavity of the reformer, and a gas channel of the heat exchanger is formed by the cylindrical cavity of the reformer; the burner is communicated with the cylindrical cavity of the reformer.

6. The system for reforming hydrogen production from methanol-water fuel of claim 5, wherein the gas passage inlet of the heat exchanger is communicated with the burner, the gas passage outlet of the heat exchanger is communicated with the gas passage inlet of the reformer, and the gas passage outlet of the reformer is communicated with the gas passage inlet of the preheater.

7. The system for reforming and producing hydrogen from methanol-water fuel according to claim 1, wherein the LTS catalytic oxidizer comprises a first housing having an air inlet and an air outlet, and a copper-zinc-based catalyst filled in the first housing; the PROX catalytic oxidation device comprises a second shell provided with an air inlet and an air outlet, and a ruthenium-based catalyst filled in the second shell.

8. The system for reforming and producing hydrogen by methanol-water fuel according to claim 7, wherein the LTS catalytic oxidizer is further provided with a gas channel for forming dividing wall type heat exchange with gas flowing through the first shell, the outlet of the gas channel of the preheater is connected with the inlet of the gas channel of the LTS catalytic oxidizer, and the outlet of the gas channel of the LTS catalytic oxidizer is connected with a combustion tail gas exhaust pipe.

9. The system for reforming and producing hydrogen by using methanol-water fuel as claimed in claim 2, wherein the outlet of the anode of the fuel cell is connected with the fuel inlet of the burner, the fuel inlet of the burner and the inlet of the PROX catalytic oxidizer are respectively connected with an air inlet pipe, and the fuel inlet of the burner is further provided with an electric heating device for heating the methanol-water fuel.

10. The system for hydrogen production by methanol-water fuel reforming as claimed in claim 1, wherein the methanol-water fuel feeding pipe and the exhaust port of the LTS catalytic oxidizer are respectively connected with a water drainage and exhaust device, and a water cooling device is further arranged on the exhaust port of the PROX catalytic oxidizer.

Technical Field

The invention belongs to the technical field of hydrogen production by reforming methanol, and particularly relates to a hydrogen production system by reforming methanol-water fuel.

Background

Energy and environment have become the primary problems facing the development of countries in the world. The emergence of hybrid electric vehicles and fuel cell vehicles which use hydrogen as an energy source provides a practical and effective solution for relieving the energy crisis and protecting the environment, and further improving the vehicle-mounted hydrogen production efficiency and providing a high-purity hydrogen source for the fuel cell gradually become the key points of attention of people. Methanol has the advantages of high hydrogen content, no sulfur, low CO content in reformate, low reaction temperature and the like, and is always an important raw material for hydrogen production by reforming. The hydrogen content of the mixed gas prepared by methanol steam reforming hydrogen production is high, and the method is the most common reforming hydrogen production method at present. The mechanism of hydrogen production by methanol steam reforming is that methanol and steam are subjected to methanol reforming reaction under the action of a catalyst to prepare hydrogen-rich mixed gas.

In the existing methanol reforming hydrogen production system, the temperature of a CO separation device is generally above 400 ℃, and a palladium membrane, a palladium alloy membrane or a palladium composite membrane is adopted. Although the palladium membrane has good selectivity to hydrogen, the palladium membrane is expensive, has serious hydrogen embrittlement phenomenon, short service life and low hydrogen permeation rate, so that the purification efficiency is low and only reaches about 75%. The palladium alloy membrane (mainly palladium-silver and palladium-yttrium alloy) has low hydrogen permeability, poor mechanical property, easy grain growth at the temperature of more than 500 ℃, short service life and can not meet the requirements of high-purity hydrogen purification and separation which are actually required. Moreover, the purification by using the palladium and palladium alloy membrane has high requirements on power equipment, the operation is required to be carried out under the pressure of more than 10bar, the capacity expansion difficulty is high, and the integral compactness of the equipment after the capacity expansion is reduced. The palladium composite membrane (supported palladium membrane) is produced by supporting a palladium metal membrane on the surface of a porous material (ceramic, quartz, stainless steel, etc.). However, although the palladium composite membrane has low cost, high purification efficiency and high yield, the purity of hydrogen separated by the palladium composite membrane is low, and the purity of the prepared hydrogen is generally only about 99 percent and is difficult to reach more than 99.999 percent.

Disclosure of Invention

In order to solve the defects in the prior art, the invention aims to provide a methanol-water fuel reforming hydrogen production system. The system of the invention abandons the existing palladium membrane separation technology, but adopts the staged catalytic oxidation purification technology to gradually reduce the CO concentration in the reformed hydrogen-rich mixed gas, finally completely remove the CO in the mixed gas, improve the purification efficiency of the hydrogen and reduce the purification cost.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

firstly, the invention provides a CO oxidation removal device, which comprises an LTS catalytic oxidation device and a PROX catalytic oxidation device, wherein a copper-zinc-based catalyst is arranged in the LTS catalytic oxidation device, and a ruthenium-based catalyst is arranged in the PROX catalytic oxidation device. The CO oxidation removal device can be used for removing CO in the reformed hydrogen-rich mixed gas, and completely oxidizing and removing the CO in the mixed gas by an LTS technology (water gas shift reaction) and a PROX technology (CO selective oxidation), wherein the process is a multi-component and multi-reaction gas-solid reaction.

Preferably, the LTS catalytic oxidizer is used for treating the hydrogen-rich mixed gas for one time to ensure that CO and H are mixed₂Reaction of O to CO₂And H₂Thereby removing most of CO in the mixed gas, and the specific reaction principle is shown in formula (1); then, the invention uses the PROX catalytic oxidizer to carry out secondary treatment on the hydrogen-rich mixed gas, and simultaneously air is introduced into the PROX catalytic oxidizer to completely remove residual CO in the mixed gas, and the specific reaction principles are shown in formulas (2) and (3).

CO+H₂O→CO₂+H₂The compound of the formula (1),

preferably, the LTS catalytic oxidizer includes a first housing provided with an air inlet and an air outlet, and a copper-zinc-based catalyst filled in the first housing. The copper zinc based catalysts are commercially available.

Preferably, the PROX catalytic oxidizer includes a second housing provided with an air inlet and an air outlet, and a ruthenium-based catalyst filled in the second housing. The ruthenium-based catalyst is commercially available.

Preferably, a cooler is arranged on the exhaust port of the LTS catalytic oxidizer. The cooler is used for cooling the hydrogen-rich mixed gas discharged by the LTS catalytic oxidizer so as to enable the hydrogen-rich mixed gas entering the PROX catalytic oxidizer to be below 200 ℃, thereby ensuring the reliability and the durability of the PROX catalytic oxidizer.

Preferably, a cooling fan is provided outside the second housing. Thereby, the reaction temperature inside the PROX catalytic oxidizer can be further reduced.

The invention further provides a methanol-water fuel reforming hydrogen production system which comprises a methanol-water fuel feeding pipe, an evaporator, a modifier, the CO oxidation removal device and a hydrogen-rich mixed gas conveying pipe which are sequentially connected. Thus, the methanol-water fuel fed from the methanol-water fuel feed pipe is heated and vaporized by the evaporator, and then enters the reformer, the reformer reforms the vaporized methanol-water fuel to generate a hydrogen-rich mixed gas, the CO oxidation and removal device then treats the hydrogen-rich mixed gas discharged from the reformer to remove CO in the mixed gas, and finally the hydrogen-rich mixed gas is fed to the fuel cell through the hydrogen-rich mixed gas feed pipe.

Preferably, the hydrogen production system by methanol-water fuel reforming further comprises a burner for heating the reformer, and a fuel inlet of the burner is connected with the methanol-water fuel feeding pipe.

Preferably, the other end (i.e., the gas outlet end) of the hydrogen-rich mixed gas delivery pipe is connected to an anode gas inlet of the fuel cell and a fuel inlet of the burner, respectively. Thereby, the hydrogen-rich mixed gas can be controlled to be supplied to the fuel cell or the combustor. When the hydrogen-rich mixed gas is transmitted to the fuel cell, the hydrogen-rich mixed gas is used for reacting with the fuel cell stack to generate electric energy. When the hydrogen-rich mixed gas is conveyed to the combustor, the hydrogen-rich mixed gas is used as fuel of the combustor to assist combustion, and the pipeline is generally opened within 1-2 min of the initial operation stage of the system, so that the reformer of the system can rapidly reach the reforming condition, and the hydrogen production by reforming is rapidly started.

Preferably, the reformer is cylindrical and provided with a jacket, a hydrogen production catalyst is filled in the jacket, the jacket is provided with a material inlet and a hydrogen-rich gas outlet, the material inlet is connected with the evaporator, and the hydrogen-rich gas outlet is connected with the air inlet of the LTS catalytic oxidizer.

Preferably, the evaporimeter is including being equipped with liquid channel and gas channel's pre-heater and heat exchanger respectively, the liquid channel entry of pre-heater with methanol-water fuel inlet pipe links to each other, the liquid channel export of pre-heater with the liquid channel entry of heat exchanger links to each other, the liquid channel export of heat exchanger with the material entry of upgrading ware links to each other. The preheater is used for heating methanol water fuel, and the heat exchanger is used for vaporizing the methanol water fuel heated by the preheater, under the combined action of the two, the rapid gasification of the methanol water fuel in the starting stage can be realized, the fuel can rapidly reach the temperature required by reforming, and the rapid starting of the reforming hydrogen production process of the system is facilitated.

Preferably, the reformer is further provided with a gas channel for exchanging heat with a jacket thereof; the heat exchanger is arranged in the cylindrical cavity of the reformer, and a gas channel of the heat exchanger is formed by the cylindrical cavity of the reformer; the burner is communicated with the cylindrical cavity of the reformer. Therefore, combustion heat generated by combustion of the combustor can be simultaneously transferred to the reformer and the heat exchanger, so that the bed layer of the reformer is heated, the liquid channel of the heat exchanger is heated, and the reformer is ensured to reach a hydrogen production condition and methanol water fuel in the liquid channel of the heat exchanger is vaporized.

Preferably, the gas passage inlet of the heat exchanger is communicated with the burner, the gas passage outlet of the heat exchanger is communicated with the gas passage inlet of the reformer, and the gas passage outlet of the reformer is communicated with the gas passage inlet of the preheater. Therefore, combustion tail gas generated by combustion of the combustor can further enter the preheater for heat exchange after heat exchange is carried out on the combustion tail gas through the heat exchanger and the reformer, and the combustion tail gas can be used as a heat source for heating methanol water fuel by the preheater.

Preferably, the LTS catalytic oxidizer is further provided with a gas channel which forms dividing wall type heat exchange with gas circulating in the first shell, an outlet of the gas channel of the preheater is connected with an inlet of the gas channel of the LTS catalytic oxidizer, and an outlet of the gas channel of the LTS catalytic oxidizer is connected with a combustion tail gas exhaust pipe. Therefore, after the combustion tail gas of the combustor enters the preheater for heat exchange to realize temperature reduction, the combustion tail gas can further enter the LTS catalytic oxidizer for heat exchange to be used as a cold source for cooling the hydrogen-rich mixed gas in the LTS catalytic oxidizer, and the effect of reducing the catalytic oxidation temperature of the LTS catalytic oxidizer is achieved.

Preferably, the anode outlet of the fuel cell is connected to the fuel inlet of the burner. Therefore, after the hydrogen-rich gas prepared by the system passes through the fuel cell stack, part of unreacted hydrogen-rich gas can be recycled through the gas pipeline and enter the combustor for combustion.

Preferably, the methanol-water fuel feeding pipe and the exhaust port of the LTS catalytic oxidizer are also respectively connected with a water drainage exhaust device. When the methanol reforming hydrogen production system is shut down or abnormally shut down, the water discharge and exhaust device can discharge methanol steam of methanol water fuel in the system in time, so that negative pressure is formed in the system, and the safety of the whole system is protected. The drainage and exhaust device can adopt the existing equipment with the drainage and exhaust functions, and the structure of the drainage and exhaust device is not limited by the invention.

Preferably, the fuel inlet of the burner and the air inlet of the PROX catalytic oxidizer are further connected to an air inlet pipe, respectively. Thus, when the burner is used for combustion and the PROX catalytic oxidizer is used for catalytic oxidation, air can be introduced into the burner to assist the combustion and the auxiliary reaction.

Preferably, the fuel inlet of the burner is further provided with an electric heating device for heating the methanol-water fuel. Therefore, in the cold start stage of the system, after the methanol-water fuel is input from the methanol-water fuel feed pipe, the methanol-water fuel can be heated and vaporized by the electric heating device and then input into the combustor to be used as fuel for combustion.

Preferably, a water cooling device is further arranged on the exhaust port of the PROX catalytic oxidizer. And the water cooling device is used for cooling the hydrogen-rich mixed gas discharged by the PROX catalytic oxidizer.

Preferably, the pipelines for conveying the methanol-water fuel and the hydrogen-rich mixed gas in the methanol-water fuel reforming hydrogen production system are provided with control valves. Thereby facilitating the feeding and discharging of the control system.

Preferably, the material inlet of the modifier is also provided with a flow limiting valve. Therefore, the methanol steam fuel after heat exchange by the heat exchanger passes through the flow limiting valve before entering the bed layer of the reformer. The methanol steam fuel can generate adiabatic expansion in the process of passing through the flow limiting valve, so that the temperature can be rapidly reduced, the temperature of the methanol steam fuel entering the reformer can not be too high, and the reforming and the modification can be carried out smoothly.

Preferably, the burner comprises an igniter and a thermocouple. When in combustion, the igniter is utilized to ignite the methanol-water fuel so as to obtain combustion heat, and the thermocouple is utilized to carry out detection and feedback so as to control the combustion temperature.

Preferably, the heat exchanger is a coil type heat exchanger, a spiral tube type heat exchanger or a brazing plate type heat exchanger.

Preferably, the methanol-water fuel is formed by mixing methanol and water in a mass ratio of 1: 1.

The work flow of the reforming hydrogen production system is as follows:

in the cold starting stage, methanol-water fuel is fed into the liquid, heated and vaporized by the electric heating device, fuel is supplied to the combustor, and methanol-water vapor is ignited to start combustion and heat supply. When the temperature of the bed layer of the reformer rises to 200-280 ℃, the control valve of the liquid channel is opened, and methanol water fuel is supplied to the reformer to carry out reforming hydrogen production. The methanol water fuel is preheated by the preheater, enters the heat exchanger for heating and gasification, and then enters the bed layer of the reformer for reforming hydrogen production. And in the initial operation stage of the system, returning the hydrogen-rich mixed gas generated by hydrogen production by reforming to the combustor for auxiliary combustion through a loop so that the reformer quickly reaches the reforming condition, quickly starting the system to produce hydrogen by reforming, and closing the loop after the system operates for 1-2 min so as to change the hydrogen-rich mixed gas into the hydrogen-rich mixed gas and transmit the hydrogen-rich mixed gas to the fuel cell. Meanwhile, after the system produces hydrogen for 1-2 min, the supply of methanol water fuel to the combustor is stopped, and unreacted H discharged by the fuel cell is recycled through a loop₂Fuel is supplied to the burner, so that the combustion of the burner is maintained, and the heat supply of the system is maintained stable.

After hydrogen-rich gas prepared by reforming methanol-water fuel passes through the fuel cell stack, part of unreacted hydrogen-rich gas, the methanol-water fuel is recovered through a gas pipeline and enters a combustor for combustion, the heat released by the combustion of the hydrogen-rich gas is utilized to heat the methanol-water fuel before entering the reformer, and the combustion tail gas is utilized to carry out primary heat exchange with the gas-liquid mixture in the heat exchanger and the reformer to heat the gas-liquid mixture therein, then the combustion tail gas enters a preheater along a gas channel for secondary heat exchange to heat the methanol-water fuel in the preheater, then the combustion tail gas enters the LTS catalytic oxidation device along the gas channel for dividing wall type heat exchange, the temperature of the hydrogen-rich mixed gas in the LTS catalytic oxidation device is reduced, therefore, the catalytic oxidation temperature of the LTS catalytic oxidizer is reduced, the purpose of removing CO by the catalyst in the LTS through low-temperature catalytic oxidation is realized, and finally, the combustion tail gas is discharged outwards after being diluted by air convection.

Compared with the prior art, the invention has the beneficial effects that:

1. the hydrogen-rich mixed gas prepared by the system is subjected to staged catalytic oxidation treatment through the LTS catalytic oxidizer and the PROX catalytic oxidizer, so that the concentration of CO in the hydrogen-rich mixed gas is gradually reduced, and the CO in the hydrogen-rich mixed gas is completely removed. The combined catalytic oxidation of LTS and PROX has good purification effect on hydrogen, high purification efficiency and low purification cost. The invention also carries out cooling temperature control treatment on the LTS catalytic oxidation stage and the PROX catalytic oxidation stage, thereby ensuring H₂The purification of (2) has reliability and durability.

2. According to the invention, through optimizing the flow paths of the liquid channel and the gas channel of the system, the tail gas of the fuel cell stack is fully recycled, the heat required by the system operation is provided by the combustion heat generated by the tail gas, meanwhile, the methanol water fuel is heated by the heat of the combustion tail gas, the heat balance of the system inside the system is maintained, the heat supply requirement of the system is met, and the combustion tail gas after heat exchange and temperature reduction can also be used as a cold source to cool the hydrogen-rich mixed gas in the LTS catalytic oxidizer, so that the CO removal effect is ensured. Therefore, the invention obviously reduces the energy consumption of the methanol reforming hydrogen production system, fully recycles the energy, and reduces the emission temperature of the combustion tail gas of the system to ensure that the emission requirement is met.

3. The conversion rate of the system to the methanol can reach 100 percent, the CO in the reformed mixed gas can be completely removed, the starting time of the system is short, the reforming hydrogen production condition can be quickly achieved, the energy consumption is low, the hydrogen production speed is high, the hydrogen production cost is low, the efficient energy conversion efficiency is realized, the environment is protected, the energy is saved, and the power generation efficiency is higher after the system is butted with a fuel cell stack.

Drawings

FIG. 1 is a schematic structural diagram of a methanol-water fuel reforming hydrogen production system according to the present invention;

FIG. 2 is a process flow diagram of a methanol-water fuel reforming hydrogen production system according to the present invention.

In the figure, a preheater 1, a heat exchanger 2, a combustor 3, a reformer 4, an LTS catalytic oxidizer 5, a PROX catalytic oxidizer 6, a combustion chamber 7, an igniter 8, a thermocouple 9, an electric heating device 10, a cooler 11, a cooling fan 12, a methanol-water fuel feed pipe 13, a fuel cell 14, a flow path 15, an air intake pipe 16, a flow path 17, a drain exhaust device 18, a gas-liquid heat exchanger 19, a cold water inlet pipe 20, a control valve 21, and a flow restriction valve 22 are shown.

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 starting materials used in the examples are commercially available and the equipment and methods used are conventional in the art unless otherwise specified.

As shown in fig. 1-2, the present embodiment provides a methanol-water fuel reforming hydrogen production system, which includes a preheater 1, a heat exchanger 2, a burner 3, a reformer 4, an LTS catalytic oxidizer 5, and a PROX catalytic oxidizer 6. Wherein the preheater 1 and the heat exchanger 2 are provided with a liquid passage and a gas passage, respectively, which can perform heat exchange. The reformer 4 is in a cylindrical shape provided with a jacket, the jacket is filled with an SCST-401 type hydrogen production catalyst, the jacket is provided with a material inlet and a hydrogen-rich gas outlet, and the reformer 4 is also provided with a gas channel for exchanging heat with the jacket. The heat exchanger 2 is disposed in the cylindrical chamber of the reformer 4, and the gas passage thereof is constituted by the cylindrical chamber. The combustor 3 comprises a combustion chamber 7, an igniter 8 and a thermocouple 9, the combustion chamber 7 is communicated with the cylindrical cavity, the igniter 8 and the thermocouple 9 are arranged in the combustion chamber, a fuel inlet is formed in the combustion chamber 7, and an electric heating device 10 is arranged on the fuel inlet.

The LTS catalytic oxidizer 5 comprises a first shell provided with an air inlet and an air outlet, and a copper-zinc-based catalyst filled in the first shell, and the LTS catalytic oxidizer has the following commercial models: the OSL-02 and LTS catalytic oxidizer 5 are provided with a cooler 11 at the exhaust port. The LTS catalytic oxidizer 5 is further provided with a gas channel which forms a dividing wall type heat exchange with the gas circulating in the first shell.

The PROX catalytic oxidizer 6 comprises a second shell provided with an air inlet and an air outlet, and a ruthenium-based catalyst filled in the second shell, and the commercial models are as follows: TSSA-5, the exterior of the second housing is provided with a cooling fan 12.

The inlet of a liquid channel of the preheater 1 is connected with a methanol water fuel feeding pipe 13, the outlet of the liquid channel of the preheater 1 is connected with the inlet of a liquid channel of the heat exchanger 2, the outlet of the liquid channel of the heat exchanger 2 is connected with the material inlet of the reformer 4, the hydrogen-rich gas outlet of the reformer 4 is connected with the gas inlet of the LTS catalytic oxidizer 5, the gas outlet of the LTS catalytic oxidizer 5 is connected with the gas inlet of the PROX catalytic oxidizer 6, and the gas outlet of the PROX catalytic oxidizer 6 is connected with the fuel inlet of the combustor 3 and the anode gas inlet of the fuel cell 14. This constitutes the flow path 15 for the methanol-water fuel and the hydrogen-rich mixed gas.

The anode gas outlet of the fuel cell 14 is connected with the combustion chamber of the combustor 3, the combustion chamber of the combustor 3 is connected with the gas channel inlet of the heat exchanger 2, the gas channel outlet of the heat exchanger 2 is connected with the gas channel inlet of the reformer 4, the gas channel outlet of the reformer 4 is connected with the gas channel inlet of the preheater 1, the gas channel outlet of the preheater 1 is connected with the gas channel inlet of the LTS catalytic oxidizer 5, and the gas channel outlet of the LTS catalytic oxidizer 5 is connected with the combustion tail gas exhaust pipe. This constitutes a flow path 17 for the fuel cell stack off-gas and the combustion off-gas.

The methanol-water fuel feeding pipe 13 and the exhaust port of the LTS catalytic oxidizer 5 are also respectively connected with the water discharging and exhausting device 18, when the methanol reforming hydrogen production system is shut down or is abnormally shut down, the water discharging and exhausting device 18 can timely discharge methanol steam of the methanol-water fuel in the system, so that negative pressure is formed in the system, and the safety of the whole system is protected.

The fuel inlet of the burner 3 and the air inlet of the PROX catalytic oxidizer 6 are also connected to an air inlet pipe 16, respectively. Thus, when the burner 3 is burning and the PROX catalytic oxidizer 6 is performing a catalytic oxidation reaction, air may be introduced to assist the combustion and assist the reaction.

And a water cooling device is also arranged on an exhaust port of the PROX catalytic oxidizer 6 and is used for cooling the hydrogen-rich mixed gas discharged from the PROX catalytic oxidizer 6. The water cooling device includes a gas-liquid heat exchanger 19, and a cold water inlet pipe 20 connected to a liquid passage of the gas-liquid heat exchanger 19.

In the hydrogen production system by reforming methanol-water fuel of the present embodiment, the pipelines for conveying methanol-water fuel and hydrogen-rich mixed gas are provided with control valves 21. Thereby facilitating the feeding and discharging of the control system.

The material inlet of the reformer 4 is also provided with a flow-limiting valve 22, so that the methanol steam fuel after heat exchange by the heat exchanger 2 passes through the flow-limiting valve to undergo adiabatic expansion before entering the bed of the reformer 4, so that the temperature is rapidly reduced, the temperature of the methanol steam fuel entering the reformer 4 is not too high, and the smooth reforming and reforming are facilitated.

The heat exchanger 2 of the embodiment can be a coil type heat exchanger, a spiral tube type heat exchanger or a brazing plate type heat exchanger. The methanol-water fuel is formed by mixing methanol and water in a mass ratio of 1: 1.

The work flow of the reforming hydrogen production system of the embodiment is as follows:

in the cold starting stage, methanol water fuel is fed, heated and vaporized by the electric heating device 10, fuel is supplied to the combustor 3, and methanol water vapor is ignited to start combustion and heat supply. When the temperature of the bed layer of the reformer 4 rises to 200-280 ℃, the control valve 21 of the liquid channel is opened, and methanol water fuel is supplied to the reformer 4 to carry out reforming hydrogen production. The methanol water fuel is preheated by a preheater 1, enters a heat exchanger 2 for heating and gasification, and then enters a bed layer of a reformer 4 for reforming hydrogen production. In the initial operation stage of the system, the hydrogen-rich mixed gas generated by reforming hydrogen production is returned to the combustor 3 for auxiliary combustion so as to make the reformer 4 fastAnd (3) quickly reaching the reforming condition, quickly starting the system to reform and produce hydrogen, and after the system runs for 1-2 min, closing the loop, and transferring the hydrogen-rich mixed gas to the fuel cell 14. Meanwhile, after the system produces hydrogen for 1-2 min, the supply of methanol water fuel to the combustor 3 is stopped, and unreacted H discharged by the fuel cell is recycled through a loop₂Fuel is supplied to the burner 3 to maintain combustion in the burner 3 and to maintain stability of heat supply in the system.

After the hydrogen-rich gas prepared by reforming the methanol-water fuel passes through the fuel cell 14 galvanic pile, part of the unreacted hydrogen-rich gas is recycled through a gas pipeline and enters the combustor 3 for combustion, the methanol-water fuel before entering the reformer 4 is heated by the heat released by the combustion of the hydrogen-rich gas, the combustion tail gas is used for carrying out primary heat exchange with the gas-liquid mixture in the heat exchanger 2 and the reformer 4 to heat the gas-liquid mixture therein, then the combustion tail gas enters the preheater 1 along a gas channel for secondary heat exchange to heat the methanol-water fuel in the preheater 1, then the combustion tail gas enters the LTS catalytic oxidizer 5 along the gas channel for dividing wall type heat exchange to reduce the temperature of the hydrogen-rich mixed gas in the LTS catalytic oxidizer 5, thereby reducing the catalytic oxidation temperature of the LTS catalytic oxidizer 5 and achieving the purpose of removing CO by the low-temperature catalytic oxidation of the catalyst in the LTS, and finally, the combustion tail gas is diluted by air convection and then is discharged outwards.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.