CN114105096B - Methanol-water reforming hydrogen production system and hydrogen production method thereof - Google Patents
Methanol-water reforming hydrogen production system and hydrogen production method thereof Download PDFInfo
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Abstract
The invention discloses a methanol-water reforming hydrogen production system which comprises a methanol-water reservoir, a heating mixing device, a reforming hydrogen production reactor, a heating device, a fuel cell device and a lithium battery, wherein the methanol-water reservoir is connected with the heating mixing device, the heating mixing device is connected with the reforming hydrogen production reactor, the methanol-water reservoir is connected with the heating device, the heating device is connected with a split device through a pipeline, the split device is connected with a hydrogen runner and an exhaust runner which penetrate through the heating mixing device and the heating device, the hydrogen runner is connected with the fuel cell device, the heating mixing device is electrically connected with the lithium battery, and the lithium battery is electrically connected with the fuel cell device. A method of producing hydrogen comprising: electrically heating; forming methanol water vapor; a methanol steam reforming reaction; splitting; heating the gas; air supply and air exhaust; the fuel cell powers. The methanol-water reforming hydrogen production system and the hydrogen production method thereof save electric energy, reuse heat and are suitable for vehicle-mounted use.
Description
Technical Field
The invention relates to the technical field of vehicle-mounted alcohol-hydrogen fuel cells, in particular to a methanol-water reforming hydrogen production system and a hydrogen production method thereof.
Background
With the recent rapid development of economy and the enhancement of environmental awareness, the concept of "hydrogen economy" has been gradually eager. The hydrogen energy automobile is rapidly developed by means of the improvement of the performance of the fuel cell, the hydrogen energy conversion efficiency is continuously improved, and the hydrogen economic benefit is continuously improved. Because of the potential hazards of hydrogen storage and transport, a great deal of research has been directed to solving this problem by way of on-site hydrogen production by an on-board hydrogen production system. Hydrogen production by methanol-water reforming hydrogen production is one of the most potential ways. In order to meet the use requirement, the method has high requirements on convenience and rapidness in vehicle-mounted hydrogen production and purity and quality of the hydrogen. Meanwhile, the comprehensive requirements of high response speed, high energy conversion efficiency, low manufacturing cost, good system integration and the like are also provided in the aspect of a hydrogen preparation system. Therefore, the development need for an integrated methanol-water reforming hydrogen production fuel cell system that can produce hydrogen with high efficiency is urgent.
While existing on-board methanol-water reforming hydrogen production fuel cell systems can fulfill the hydrogen demand for hydrogen production, there are many drawbacks. The main problems are as follows: 1. because the methanol-water reforming hydrogen production reaction is a strong endothermic reaction, the methanol-water reforming hydrogen production reaction needs to provide a large amount of heat, a reliable and efficient vehicle thermal management route is lacked on a vehicle, the systematic requirement of the methanol-water reforming reaction is difficult to meet, the current thermal management of the methanol-water reforming hydrogen production mainly takes a single device of a hydrogen production reactor as a main device, other devices of the system are not considered enough, the heat loss of the system is more, the heat of the system is not matched with the heat of other devices for use, and the thermal efficiency of the system is lower and the economy is poor when the vehicle is used; 2. the methanol-water reforming hydrogen production system has a large amount of high-temperature waste gas discharged, so that heat is wasted, and the overall energy utilization rate of the system is reduced.
In summary, the existing vehicle-mounted methanol-water reforming hydrogen production fuel cell system still has a plurality of defects, and in order to globally solve the problems of low heat utilization rate, low heating efficiency, low heating effect and the like of the existing system, the application provides a novel electric heating methanol-water reforming hydrogen production system and a hydrogen production method thereof.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a methanol-water reforming hydrogen production system and a hydrogen production method thereof, which are used for realizing the gradient utilization of the discharged high-temperature heat, saving electric energy, realizing the reutilization of reaction heat, improving the heating efficiency and the heating effect and being suitable for vehicle-mounted use.
In order to solve the technical problems, the invention adopts the following technical scheme:
the utility model provides a methanol-water reforming hydrogen manufacturing system, includes methanol-water reservoir, heating mixing arrangement, reforming hydrogen manufacturing reactor, heating device, fuel cell device and lithium cell, be connected with first pipeline between methanol-water reservoir and the heating mixing arrangement, be connected with the second pipeline between heating mixing arrangement and the reforming hydrogen manufacturing reactor, be connected with the third pipeline between methanol-water reservoir and the heating device, be connected with the fourth pipeline between heating device and the heating mixing arrangement, reforming hydrogen manufacturing reactor exit linkage has diverging device, diverging device's exit linkage has hydrogen runner and exhaust gas flow path, the hydrogen runner wears to locate in heating mixing arrangement and the heating device in proper order, just the exit end of hydrogen runner is connected with fuel cell device, exhaust gas flow path wears to locate in heating mixing arrangement and the heating device in proper order, heating mixing arrangement and reforming hydrogen manufacturing reactor are connected with the lithium cell electricity respectively, lithium cell and fuel cell device electricity are connected.
As a further improvement of the above technical scheme:
and a first regulating valve is arranged on the second pipeline.
And the hydrogen flow passage and the waste gas flow passage are respectively provided with a second regulating valve.
The first pipeline is provided with a first water pump, the third pipeline is provided with a second water pump, and the fourth pipeline is provided with a third regulating valve.
The reforming hydrogen production reactor is internally provided with a preheating section and a reaction section, a reaction channel is arranged in the reaction section, a catalyst layer is coated on the inner wall of the reaction channel, the second pipeline is communicated with the preheating section, the inlet of the reaction channel is communicated with the preheating section, and the outlet of the reaction channel is communicated with the flow dividing device.
The methanol-water reforming hydrogen production system further comprises a cooling water circulation device, a cooling water flow channel and a backwater flow channel, wherein the cooling flow channel is arranged in the fuel cell device, one end of the cooling water flow channel is connected with an outlet of the cooling water circulation device, the other end of the cooling water flow channel is connected with a water inlet end of the cooling flow channel, one end of the backwater flow channel is connected with an inlet of the cooling water circulation device, and the other end of the backwater flow channel is connected with a water outlet end of the cooling flow channel.
The backwater flow passage penetrates through the heating device.
The hydrogen production method is carried out by adopting the methanol-water reforming hydrogen production system and comprises a starting stage and a stable operation stage;
the start-up phase comprises the following steps:
s1, electric heating: the heating and mixing device is powered by a lithium battery to heat to a temperature T1; the reforming hydrogen production reactor is powered by a lithium battery to be heated to the temperature T2 at which the reforming reaction of the methanol and the water vapor occurs;
s2, forming methanol water vapor: the normal temperature methanol water in the methanol water storage is conveyed to a heating and mixing device, and methanol water vapor is formed in the heating and mixing device;
s3, methanol steam reforming reaction: introducing methanol steam into a reforming hydrogen production reactor to perform a methanol steam reforming reaction to generate hydrogen-rich mixed gas;
s4, splitting: the hydrogen-rich mixed gas is split into hydrogen and waste gas by a splitting device, the hydrogen enters a hydrogen flow channel, and the waste gas enters a waste gas flow channel;
s5, heating gas: the hydrogen and the waste gas respectively pass through the hydrogen flow passage and the waste gas flow passage in sequence in the heating and mixing device and the heating device, so that the heating device is heated to the temperature T3, and the heating and mixing device is kept at the temperature T1;
s6, supplying hydrogen and discharging waste gas: hydrogen enters the fuel cell device from the outlet end of the hydrogen flow passage to supply hydrogen for the fuel cell device; the exhaust gas is discharged from the outlet end of the exhaust gas flow channel;
the steady operation phase comprises the following steps:
s7, the fuel cell device charges a lithium battery; the normal temperature methanol water in the methanol water storage is heated to T3 by the heating device and then sent to the heating and mixing device.
As a further improvement of the above technical scheme:
the temperature of T1 is 105-115 ℃, and the temperature of T3 is 35-45 ℃.
The mass ratio of water to methanol in the methanol water reservoir is 1.1-1.5.
Compared with the prior art, the invention has the advantages that:
in the stable operation stage of the methanol-water reforming hydrogen production system, the heating mixing device only needs low-power discharge of the lithium battery to carry out accurate temperature adjustment heating, and the high-temperature hydrogen-rich mixed gas generated by the reaction of the reforming hydrogen production reactor is mainly used as a heat source of the heating mixing device and a heat source of the heating device so as to realize the heating functions of the heating mixing device and the heating device, save electric energy and recycle the reaction heat. In addition, hydrogen passes through the hydrogen runner and sequentially passes through the heating mixing device and the heating device, and waste gas passes through the waste gas runner and sequentially passes through the heating mixing device and the heating device, namely, the hydrogen and the waste gas firstly enter the heating mixing device to exchange heat and cool down, and then the heating device exchanges heat, so that the gradient utilization of temperature is formed, which is equivalent to the preheating of methanol water to T3 in the heating device before entering the heating mixing device, and the heating efficiency and the heating effect are improved. The methanol-water reforming hydrogen production system saves electric energy, realizes the reutilization of reaction heat, improves the heating efficiency and the heating effect, and is suitable for vehicle-mounted use.
In the stable operation stage of the hydrogen production method, the heating mixing device only needs low-power discharge of the lithium battery to carry out accurate temperature adjustment heating, and the high-temperature hydrogen-rich mixed gas generated by the reaction of the reforming hydrogen production reactor is mainly used as a heat source of the heating mixing device and the heating device so as to realize the heating function of the heating mixing device and the heating device, thereby saving electric energy and realizing the reutilization of reaction heat. In addition, hydrogen passes through the hydrogen runner and sequentially passes through the heating mixing device and the heating device, and waste gas passes through the waste gas runner and sequentially passes through the heating mixing device and the heating device, namely, the hydrogen and the waste gas firstly enter the heating mixing device to exchange heat and cool down, and then the heating device exchanges heat, so that the gradient utilization of temperature is formed, which is equivalent to the preheating of methanol water to T3 in the heating device before entering the heating mixing device, and the heating efficiency and the heating effect are improved. The hydrogen production method saves electric energy, realizes the reutilization of reaction heat, improves heating efficiency and heating effect, and is suitable for vehicle-mounted use.
Drawings
FIG. 1 is a schematic diagram of a methanol-water reforming hydrogen production system of the present invention.
Fig. 2 is a schematic diagram of the hydrogen production process of the present invention at a start-up stage.
FIG. 3 is a schematic diagram of the hydrogen production process of the present invention during a steady state operation.
The reference numerals in the drawings denote:
1. a methanol water reservoir; 11. a first pipe; 111. a first water pump; 12. a third conduit; 121. a second water pump; 2. heating the mixing device; 21. a second pipe; 211. a first regulating valve; 3. a reforming hydrogen production reactor; 31. a preheating section; 32. a reaction section; 321. a reaction channel; 4. a heating device; 41. a fourth conduit; 411. a third regulating valve; 5. a fuel cell device; 6. a lithium battery; 7. a shunt device; 71. a hydrogen flow passage; 72. a waste gas flow path; 73. a second regulating valve; 8. a cooling water circulation device; 9. a cooling water flow passage; 91. and a backwater flow passage.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples.
Embodiment one:
fig. 1 shows an embodiment of a methanol-water reforming hydrogen production system of the invention, the methanol-water reforming hydrogen production system comprises a methanol-water reservoir 1, a heating mixing device 2, a reforming hydrogen production reactor 3, a heating device 4, a fuel cell device 5 and a lithium battery 6, wherein a first pipeline 11 is connected between the methanol-water reservoir 1 and the heating mixing device 2, a second pipeline 21 is connected between the heating mixing device 2 and the reforming hydrogen production reactor 3, a third pipeline 12 is connected between the methanol-water reservoir 1 and the heating device 4, a fourth pipeline 41 is connected between the heating device 4 and the heating mixing device 2, an outlet of the reforming hydrogen production reactor 3 is connected with a flow dividing device 7, an outlet of the flow dividing device 7 is connected with a hydrogen runner 71 and an exhaust runner 72, the hydrogen runner 71 sequentially penetrates through the heating mixing device 2 and the heating device 4, an outlet end of the hydrogen runner 71 is connected with the fuel cell device 5, a waste runner 72 sequentially penetrates through the heating mixing device 2 and the heating device 4, the heating mixing device 2 and the reforming hydrogen production reactor 3 are respectively electrically connected with the lithium battery 6, and the lithium battery 6 is electrically connected with the fuel cell device 5.
Hydrogen production process: first entering the start-up phase and then entering the steady operation phase. A starting stage: the heating and mixing device 2 is powered by the lithium battery 6 to heat to a temperature T1, and the reforming hydrogen production reactor 3 is powered by the lithium battery 6 to heat to a temperature T2 at which a methanol steam reforming reaction occurs; then, the normal temperature methanol water in the methanol water reservoir 1 is sent to the heating and mixing device 2, and methanol water vapor is formed in the heating and mixing device 2; the methanol vapor in the heating and mixing device 2 is then introduced into the reforming hydrogen production reactor 3, and the reforming hydrogen production reactor 3 carries out the reforming reaction of the methanol vapor to generate hydrogen-rich mixed gas; the hydrogen-rich mixed gas flows out from an outlet of the reforming hydrogen production reactor 3 and is split into hydrogen and waste gas through the splitting device 7, the hydrogen enters the hydrogen flow passage 71, the waste gas enters the waste gas flow passage 72, the hydrogen sequentially passes through the heating mixing device 2 and the heating device 4 through the hydrogen flow passage 71, and the waste gas sequentially passes through the heating mixing device 2 and the heating device 4 through the waste gas flow passage 72, so that the heating device 4 is heated to a temperature T3, and the heating mixing device 2 is kept at the temperature T1; hydrogen enters the fuel cell device 5 from the outlet end of the hydrogen flow passage 71 to supply hydrogen to the fuel cell device 5; exhaust gas exits from the outlet end of the exhaust gas flow passage 72. Stable operation phase: the fuel cell device 5 charges the lithium battery 6; the normal temperature methanol water in the methanol water storage 1 is heated to T3 by the heating device 4 and then sent to the heating and mixing device 2, and methanol water vapor is formed in the heating and mixing device 2; the methanol vapor in the heating and mixing device 2 is then introduced into the reforming hydrogen production reactor 3, and the reforming hydrogen production reactor 3 carries out the reforming reaction of the methanol vapor to generate hydrogen-rich mixed gas; the hydrogen-rich mixed gas flows out from an outlet of the reforming hydrogen production reactor 3 and is split into hydrogen and waste gas through the splitting device 7, the hydrogen enters the hydrogen flow passage 71, the waste gas enters the waste gas flow passage 72, the hydrogen sequentially passes through the heating mixing device 2 and the heating device 4 through the hydrogen flow passage 71, and the waste gas sequentially passes through the heating mixing device 2 and the heating device 4 through the waste gas flow passage 72, so that the heating device 4 is heated to a temperature T3, and the heating mixing device 2 is kept at the temperature T1; hydrogen enters the fuel cell device 5 from the outlet end of the hydrogen flow passage 71 to supply hydrogen to the fuel cell device 5; exhaust gas exits from the outlet end of the exhaust gas flow passage 72.
In the stable operation stage of the methanol-water reforming hydrogen production system, the heating mixing device 2 only needs to carry out accurate temperature adjustment heating by means of low-power discharge of the lithium battery 6, and the high-temperature hydrogen-rich mixed gas (more than 110 ℃) generated by the reaction of the reforming hydrogen production reactor 3 is mainly used as a heat source for heating the mixing device 2 and the heating device 4, so that the heating functions of the heating mixing device 2 and the heating device 4 are realized, electric energy is saved, and the reutilization of reaction heat is realized. In addition, the hydrogen passes through the hydrogen flow passage 71 and then passes through the heating and mixing device 2 and the heating device 4, the waste gas passes through the waste gas flow passage 72 and then passes through the heating and mixing device 2 and the heating device 4, namely, the hydrogen and the waste gas firstly enter the heating and mixing device 2 to exchange heat and cool, and then the heating device 4 exchanges heat, so that the gradient utilization of the temperature is formed, which is equivalent to the preheating of the methanol water to T3 in the heating device 4 before entering the heating and mixing device 2, and the heating efficiency and the heating effect are improved. The methanol-water reforming hydrogen production system saves electric energy, realizes the reutilization of reaction heat, improves the heating efficiency and the heating effect, and is suitable for vehicle-mounted use.
In this embodiment, the second pipe 21 is provided with a first regulating valve 211. The flow of the methanol vapor of the reforming hydrogen production reactor 3 is regulated by the first regulating valve 211, so that the requirement of the reforming hydrogen production reactor 3 on the inlet amount of the methanol vapor is met.
In this embodiment, the hydrogen flow path 71 and the exhaust flow path 72 are each provided with a second regulating valve 73. The second regulating valve 73 controls the flow rates of the hydrogen-saving flow path 71 and the exhaust flow path 72, thereby achieving the effect of controlling the temperatures of the heating and mixing device 2 and the heating device 4, heating the heating device 4 to the temperature T3, and maintaining the temperature T1 of the heating and mixing device 2.
In this embodiment, the first pipe 11 is provided with a first water pump 111, the third pipe 12 is provided with a second water pump 121, and the fourth pipe 41 is provided with a third regulating valve 411. In the start-up phase, the first water pump 111 is turned on, the second water pump 121 is turned off, and the normal-temperature methanol water in the methanol water reservoir 1 is fed into the heating and mixing device 2 through the first water pump 111. In the steady operation phase: the first water pump 111 is turned off, the second water pump 121 is turned on, and the normal-temperature methanol water in the methanol water reservoir 1 is sent to the heating device 4 through the second water pump 121, preheated to T3 by the heating device 4, and then sent to the heating and mixing device 2.
In this embodiment, a preheating section 31 and a reaction section 32 are disposed in the reforming hydrogen production reactor 3, a reaction channel 321 is disposed in the reaction section 32, a catalyst layer is coated on the inner wall of the reaction channel 321, the second pipeline 21 is communicated with the preheating section 31, the inlet of the reaction channel 321 is communicated with the preheating section 31, and the outlet is communicated with the flow dividing device 7. The reforming hydrogen production reactor 3 firstly carries out temperature regulation and control on the methanol-water mixed steam in the preheating section 31 so as to reach the temperature range (230 ℃ to 270 ℃ of the copper-based catalyst and 350 ℃ to 500 ℃ of the platinum-palladium catalyst) in which the efficient catalytic reaction of the catalyst occurs. Then, the methanol-water mixed vapor enters the reaction channel 321 in the reaction section 32 to carry out the methanol-water vapor reforming reaction, wherein the reaction channel 321 is filled with a catalyst, and the catalyst can be selected from a common cylinder or is prepared by a sol-gel method and then coated on the inner surface of the reaction channel 321 to form a catalyst layer. In which the main chemical reactions take place are
Note that: in the starting stage, before the methanol-water mixed steam enters the reforming hydrogen production reactor 3, the reforming hydrogen production reactor 3 is driven by the lithium battery 6 to heat up to reach the high-efficiency reaction temperature range of the catalyst (for example, the high-efficiency reaction temperature range of the copper-based catalyst is 230-270 ℃, and the high-efficiency reaction temperature range of the platinum-palladium catalyst is 350-500 ℃).
In this embodiment, the hydrogen production system by reforming methanol water further includes a cooling water circulation device 8, a cooling water flow channel 9 and a backwater flow channel 91, wherein the cooling flow channel is arranged in the fuel cell device 5, one end of the cooling water flow channel 9 is connected with an outlet of the cooling water circulation device 8, the other end is connected with a water inlet end of the cooling flow channel, one end of the backwater flow channel 91 is connected with an inlet of the cooling water circulation device 8, and the other end is connected with a water outlet end of the cooling flow channel. The cooling water flow channel 9 forms a loop with the fuel cell device 5 through the cooling water flow channel 9 and the backwater flow channel 91, so as to cool the fuel cell device 5 and prolong the service life of the fuel cell device 5.
In this embodiment, the water return channel 91 is disposed through the heating device 4. After passing through the fuel cell device 5, the cooling water in the cooling water channel 9 is heated to 50-70 ℃, then enters the heating device 4 through the backwater channel 91 for heat exchange, so that the heating device 4 is heated, and finally returns to the cooling water circulation device 8. The hydrogen gas, the exhaust gas and the high-temperature cooling water (50-70 ℃) discharged from the fuel cell device 5 are introduced into the heating device 4 as a heat source for heating the methanol-water mixture, and the temperature of the methanol-water mixture introduced into the heating device 4 is adjusted and heated to T3 (35-45 ℃) by appropriately controlling the flow rate.
The methanol-water reforming hydrogen production system is applied to vehicles, namely, is used as a vehicle. The lithium battery 6 is a battery configured for a vehicle.
Embodiment two:
FIGS. 2 and 3 illustrate one embodiment of the hydrogen production process of the present invention, using the methanol water reforming hydrogen production system described above, including a start-up phase and a steady-state operation phase;
the starting phase comprises the following steps:
s1, electric heating: the heating and mixing device 2 is powered by the lithium battery 6 to heat to a temperature T1; the reforming hydrogen production reactor 3 is powered by the lithium battery 6 to be heated to the temperature T2 at which the reforming reaction of the methanol steam occurs;
s2, forming methanol water vapor: the normal temperature methanol water in the methanol water reservoir 1 is delivered to the heating and mixing device 2, and methanol water vapor is formed in the heating and mixing device 2;
s3, methanol steam reforming reaction: introducing methanol steam into a reforming hydrogen production reactor 3 to perform a methanol steam reforming reaction to generate hydrogen-rich mixed gas;
s4, splitting: the hydrogen-rich mixed gas is split into hydrogen and waste gas by the splitting device 7, the hydrogen enters the hydrogen flow passage 71, and the waste gas enters the waste gas flow passage 72;
s5, heating gas: the hydrogen and the waste gas respectively pass through the hydrogen flow passage 71 and the waste gas flow passage 72 in sequence in the heating and mixing device 2 and the heating device 4, so that the heating device 4 is heated to the temperature T3, and the heating and mixing device 2 is kept at the temperature T1;
s6, supplying hydrogen and discharging waste gas: hydrogen enters the fuel cell device 5 from the outlet end of the hydrogen flow passage 71 to supply hydrogen to the fuel cell device 5; exhaust gas is discharged from the outlet end of the exhaust gas flow passage 72;
the steady operation phase comprises the following steps:
s7, the fuel cell device 5 charges the lithium battery 6; the normal temperature methanol water in the methanol water reservoir 1 is heated to T3 by the heating device 4 and then sent to the heating and mixing device 2. When the fuel cell device 5 is added to charge the lithium battery 6 and stably operates, the fuel cell device 5 is used as a main electric energy source, the lithium battery 6 is used as an electric power source in a starting stage, and in vehicle-mounted actual use, only a small-power lithium battery is needed. The fuel cell device 5 cannot be directly powered and needs to be completed by a lithium battery 6.
In the hydrogen production method, in the steady operation stage, the heating and mixing device 2 only needs to carry out accurate temperature adjustment heating by means of low-power discharge of the lithium battery 6, and the heat sources of the heating and mixing device 2 and the heating device 4 are mainly used for heating the high-temperature hydrogen-rich mixed gas (more than 110 ℃) generated by the reaction of the reforming hydrogen production reactor 3, so that the heating functions of the heating and mixing device 2 and the heating device 4 are realized, the electric energy is saved, and the reutilization of the reaction heat is realized. In addition, the hydrogen passes through the hydrogen flow passage 71 and then passes through the heating and mixing device 2 and the heating device 4, the waste gas passes through the waste gas flow passage 72 and then passes through the heating and mixing device 2 and the heating device 4, namely, the hydrogen and the waste gas firstly enter the heating and mixing device 2 to exchange heat and cool, and then the heating device 4 exchanges heat, so that the gradient utilization of the temperature is formed, which is equivalent to the preheating of the methanol water to T3 in the heating device 4 before entering the heating and mixing device 2, and the heating efficiency and the heating effect are improved. The hydrogen production method saves electric energy, realizes the reutilization of reaction heat, improves heating efficiency and heating effect, and is suitable for vehicle-mounted use.
In this example, T1 is 105℃to 115℃and T3 is 35℃to 45 ℃.
In this embodiment, the mass ratio of water to methanol in the methanol water reservoir 1 is 1.1 to 1.5.
The hydrogen production method is applied to a vehicle, and the lithium battery 6 is a battery configured for the vehicle.
In the vehicle start-up phase, normal temperature methanol water (20 ℃ to 30 ℃, preferably 25 ℃) in the methanol water storage 1 is firstly conveyed to the heating and mixing device 2 (driven by the vehicle-mounted lithium battery 6) through the first water suction pump 111 (driven by the vehicle-mounted lithium battery 6), and the methanol water mixed solution at normal temperature is heated to a mixed gas state (105 ℃ to 115 ℃, preferably 110 ℃) by the heating and mixing device 2, so that the first-stage heating is completed. The main function of the heating and mixing device 2 is to heat the methanol-water mixed solution and avoid separation of methanol and water caused by different boiling points of the methanol and the water, and the outlet end of the heating and mixing device 2 can still ensure that the methanol-water vapor is formed according to the proportion in the vehicle-mounted methanol-water storage 1. And then controlling a first regulating valve 211 at the outlet end of the heating and mixing device 2 to introduce the mixed methanol vapor into the vehicle-mounted reforming hydrogen production reactor 3, wherein the vehicle-mounted reforming hydrogen production reactor 3 (driven by a vehicle-mounted lithium battery 6) firstly regulates the temperature of the mixed methanol vapor in a preheating section 31 (second-stage heating) so as to reach the temperature range (230-270 ℃ of a copper-based catalyst and 350-500 ℃ of a platinum-palladium catalyst) in which the efficient catalytic reaction of the catalyst occurs. The methanol-water mixed vapor enters the reaction channel 321 in the reaction section 32 to carry out the methanol-water vapor reforming reaction, wherein the reaction channel 321 is filled with a catalyst, and the catalyst can be selected from a common cylinder or prepared by a sol-gel method and then coated on the inner surface of the reaction channel 321 to form a catalyst layer. In which the main chemical reactions take place are
Note that: before the methanol-water mixed steam enters the reforming hydrogen production reactor 3, the reforming hydrogen production reactor 3 is driven by the lithium battery 6 to heat up to reach the high-efficiency reaction temperature range of the catalyst (for example, the high-efficiency reaction temperature range of the copper-based catalyst is 230-270 ℃, and the high-efficiency reaction temperature range of the platinum-palladium catalyst is 350-500 ℃).
And then purifying and splitting high-temperature mixed gas generated at the outlet end of the vehicle-mounted reforming hydrogen production reactor 3 into two circulating pipelines (a hydrogen flow passage 71 and an exhaust flow passage 72) of high-purity hydrogen and exhaust gas by a splitting device, enabling the gas of the two circulating pipelines to pass through the high-temperature gas flow passage of the heating and mixing device 2, taking the high-temperature gas introduced into the heating and mixing device 2 as a heat source for heating the aqueous solution of methanol, heating the aqueous solution of methanol in the heating and mixing device 2 to 105-115 ℃ by matching with discharge control of a lithium battery 6 through proper flow control, and forming methanol-water mixed steam, wherein in order to avoid separation of methanol and water due to different boiling points (the boiling point of methanol is 64.7 ℃ under normal pressure, and the boiling point of water is 100 ℃), disturbance in the heating and mixing device 2 is driven by the vehicle-mounted lithium battery 6. Then, the hydrogen and the waste gas (105-115 ℃) which flow out of the outlet end of the high-temperature gas flow channel of the heating mixing device 2 are led into the heating device 4, three high-temperature gas flow channels are designed in the heating device 4 and are respectively used for leading in the hydrogen and the waste gas which flow out of the heating mixing device 2 and the high-temperature cooling water (50-70 ℃) which are discharged by the fuel cell device 5, wherein the high-temperature gas which is led into the heating device 4 is used as a heat source for heating the methanol-water mixed liquid, the temperature of the methanol-water mixed liquid which is led into the heating device 4 is regulated to be between 35 and 45 ℃ by properly controlling the flow rate, the waste gas is discharged into the air at the outlet end of the heating device 4, the hydrogen (35-45 ℃) is led into the fuel cell device 5 to be used as a main energy supply device of the whole vehicle, and meanwhile, the cooling water (35-45 ℃) is refluxed to the main cooling water channel of the fuel cell device 5, so that the cooling water can circulate in the whole loop.
In a stable operation state, methanol water added into the vehicle-mounted methanol-water storage 1 in a certain proportion (the mass ratio of water to alcohol is 1-1.5) is conveyed into the heating device 4 through the second water suction pump 121, cooling water, waste gas and hydrogen gas are heated to 35-45 ℃ in the heating device 4 (first-stage heating), then the mixture is controlled to flow out into the heating and mixing device 2 through the third regulating valve 411 at the outlet end of the heating device 4, the mixture is heated in the heating and mixing device 2 through high-temperature high-purity hydrogen gas, high-temperature waste gas and a heating module in the heating and mixing device 2 supplied by discharging of the fuel cell device 5, the methanol-water temperature is regulated and controlled to reach 105-115 ℃ (second-stage heating), the mixed methanol-water vapor which is uniformly mixed with the vehicle-mounted methanol-water storage 1 in proportion is formed, then the high-temperature mixed methanol-water vapor is controlled to flow into the vehicle-mounted hydrogen production reforming reactor 3 through the first regulating valve 211 at the outlet end of the heating and mixing device 2 (driven by the vehicle-mounted fuel cell device 5), the temperature of the methanol-water mixed methanol-steam is firstly heated in the preheating section 31 (third-stage heating), so that the high-efficiency palladium catalyst reaches the temperature range of the methanol-based catalyst (the platinum catalyst is regulated and controlled to reach the temperature range of between 230 ℃ and the methanol-catalyst in the hydrogen production system and the stable reaction mode of the reaction system and the temperature of 270 ℃ in the methanol-based catalyst at the temperature of the methanol-reforming stage of the reaction system and the stable reaction mode of the temperature of the methanol-based catalyst at the temperature of the catalyst and at the temperature of between the catalyst and 270 ℃ and between the temperature and the methanol-stable reaction stage and the temperature.
While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art, or equivalent embodiments with equivalent variations can be made, without departing from the scope of the invention. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall fall within the scope of the technical solution of the present invention.
Claims (10)
1. A methanol-water reforming hydrogen production system, characterized in that: the hydrogen production device comprises a methanol water storage device (1), a heating mixing device (2), a reforming hydrogen production reactor (3), a heating device (4), a fuel cell device (5) and a lithium battery (6), wherein a first pipeline (11) is connected between the methanol water storage device (1) and the heating mixing device (2), a second pipeline (21) is connected between the heating mixing device (2) and the reforming hydrogen production reactor (3), a third pipeline (12) is connected between the methanol water storage device (1) and the heating device (4), a fourth pipeline (41) is connected between the heating device (4) and the heating mixing device (2), a flow dividing device (7) is connected to an outlet of the reforming hydrogen production reactor (3), a hydrogen flow passage (71) and an exhaust flow passage (72) are sequentially arranged in the heating mixing device (2) and the heating device (4), an outlet end of the hydrogen flow passage (71) is connected with the fuel cell device (5), an exhaust flow passage (72) is sequentially arranged in the heating mixing device (2) and the heating device (4) and the lithium battery (3) in a mixing device (6) and the heating device (3) in a penetrating mode, the lithium battery (6) is electrically connected to the fuel cell device (5).
2. The methanol-water reforming hydrogen production system as in claim 1 wherein: the second pipeline (21) is provided with a first regulating valve (211).
3. The methanol-water reforming hydrogen production system as in claim 2 wherein: the hydrogen flow passage (71) and the exhaust flow passage (72) are respectively provided with a second regulating valve (73).
4. A methanol-water reforming hydrogen production system as in claim 3 wherein: the first pipeline (11) is provided with a first water pump (111), the third pipeline (12) is provided with a second water pump (121), and the fourth pipeline (41) is provided with a third regulating valve (411).
5. The methanol-water reforming hydrogen production system as in claim 1 wherein: the reforming hydrogen production reactor is characterized in that a preheating section (31) and a reaction section (32) are arranged in the reforming hydrogen production reactor (3), a reaction channel (321) is arranged in the reaction section (32), a catalyst layer is coated on the inner wall of the reaction channel (321), the second pipeline (21) is communicated with the preheating section (31), an inlet of the reaction channel (321) is communicated with the preheating section (31), and an outlet of the reaction channel is communicated with the flow dividing device (7).
6. A methanol-water reforming hydrogen production system as in any one of claims 1 to 5 wherein: the methanol-water reforming hydrogen production system further comprises a cooling water circulation device (8), a cooling water flow channel (9) and a backwater flow channel (91), wherein the cooling flow channel is arranged in the fuel cell device (5), one end of the cooling water flow channel (9) is connected with an outlet of the cooling water circulation device (8), the other end of the cooling water flow channel is connected with a water inlet end of the cooling flow channel, one end of the backwater flow channel (91) is connected with an inlet of the cooling water circulation device (8), and the other end of the backwater flow channel is connected with a water outlet end of the cooling flow channel.
7. The methanol-water reforming hydrogen production system as in claim 6 wherein: the backwater flow passage (91) is arranged in the heating device (4) in a penetrating way.
8. A method for producing hydrogen, characterized by: use of a methanol-water reforming hydrogen production system as in any one of claims 1 to 7 comprising a start-up phase and a steady-state operation phase; firstly, entering a starting stage, and then entering a stable operation stage;
the start-up phase comprises the following steps:
s1, electric heating: the heating and mixing device (2) is powered by a lithium battery (6) to heat to a temperature T 1 The method comprises the steps of carrying out a first treatment on the surface of the The reforming hydrogen production reactor (3) is powered by a lithium battery (6) to be heated to the temperature T at which the reforming reaction of the methanol and the water vapor occurs 2 ；
S2, forming methanol water vapor: the normal-temperature methanol water in the methanol water storage (1) is conveyed to the heating and mixing device (2), and methanol water vapor is formed in the heating and mixing device (2);
s3, methanol steam reforming reaction: introducing methanol steam into a reforming hydrogen production reactor (3) to perform a methanol steam reforming reaction to generate hydrogen-rich mixed gas;
s4, splitting: the hydrogen-rich mixed gas is split into hydrogen and waste gas by a splitting device (7), the hydrogen enters a hydrogen flow passage (71), and the waste gas enters a waste gas flow passage (72);
s5, heating gas: the hydrogen and the waste gas respectively pass through a hydrogen flow passage (71) and an waste gas flow passage (72) in sequence and are heated in a heating mixing device (2) and a heating device (4), so that the heating device (4) is heated to the temperature T 3 The heating and mixing device (2) is kept at a temperature T 1 ；
S6, supplying hydrogen and discharging waste gas: hydrogen enters the fuel cell device (5) from the outlet end of the hydrogen flow passage (71) to supply hydrogen for the fuel cell device (5); exhaust gas is discharged from an outlet end of the exhaust gas flow passage (72);
the steady operation phase comprises the following steps:
s7, charging a lithium battery (6) by the fuel cell device (5), and heating normal-temperature methanol water in the methanol water storage (1) to T by the heating device (4) 3 Then, the mixture is sent to a heating and mixing device (2); the high-temperature hydrogen-rich mixed gas generated by the reaction of the reforming hydrogen production reactor (3) is mainly used as a heat source of the heating mixing device (2) and the heating device (4), so that the heating functions of the heating mixing device (2) and the heating device (4) are realized.
9. The method of producing hydrogen of claim 8, wherein: the T is 1 105-115 ℃, T is as follows 3 The temperature is 35-45 ℃.
10. The method of producing hydrogen of claim 9, wherein: the mass ratio of water to methanol in the methanol water reservoir (1) is 1.1-1.5.
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