CN105152133A - Online high-purity hydrogen preparation system for fuel cell and control method of online high-purity hydrogen preparation system - Google Patents
Online high-purity hydrogen preparation system for fuel cell and control method of online high-purity hydrogen preparation system Download PDFInfo
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- CN105152133A CN105152133A CN201510558853.1A CN201510558853A CN105152133A CN 105152133 A CN105152133 A CN 105152133A CN 201510558853 A CN201510558853 A CN 201510558853A CN 105152133 A CN105152133 A CN 105152133A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses an online high-purity hydrogen preparation system for a fuel cell. The online high-purity hydrogen preparation system comprises a methyl alcohol box as well as a raw material box and a catalytic burner which are connected with the methyl alcohol box through a methyl alcohol metering pump, wherein a fuel cell discharge water inlet is formed in the raw material box, an oxygen inlet is formed in the catalytic burner, an ethanol water metering pump and a heat exchanger are sequentially connected onto the raw material box, a vaporizer is connected onto the heat exchanger, a reforming reactor is connected onto the vaporizer, a palladium film purifier is connected onto the reforming reactor, and the palladium film purifier is connected with the catalytic burner; the invention further discloses a control method of the system. According to the system provided by the invention, online hydrogen supplying is performed through a manner of using a methanol water reforming reaction to produce hydrogen, the yield of pure hydrogen is controlled through adjusting the flow of an ethanol water mixture; the method has the characteristics of high hydrogen storage density, high hydrogen purity, low energy consumption, compact structure, simpleness and convenience in start-stop controlling, easiness in implementing modular design and the like.
Description
Technical field
The invention belongs to online hydrogen producing technology field, relate to a kind of online hydrogen generating system for Proton Exchange Membrane Fuel Cells, and control method.
Background technology
Fuel cell is a kind of efficient generating apparatus without combustion processes.Fuel cell is different with traditional battery, and the chemical energy be stored in fuel and oxygenant is directly converted into electric energy by electrochemical means by it.Fuel cell has a lot of type, can be divided into by electrolytical difference: alkaline fuel cell, phosphoric acid type fuel cell, molten carbonate fuel cell, Proton Exchange Membrane Fuel Cells and Solid Oxide Fuel Cell etc.Wherein, Proton Exchange Membrane Fuel Cells is compared with the fuel cell of other types, has high power density, high-energy conversion efficiency, low-vibration noise, cold-starting, advantages of environment protection.At present, Proton Exchange Membrane Fuel Cells has been widely used in the fields such as clean energy, traffic, distributed power station, emergency source of electric power, defence and military.
High-purity hydrogen is the fuel of Proton Exchange Membrane Fuel Cells.The method that high-purity hydrogen is prepared in industrial mass-producing is mainly water electrolysis hydrogen producing, hydrogen making by natural gas reformation etc.When Proton Exchange Membrane Fuel Cells is as power generation system, high-purity hydrogen is stored in specific device usually, and the operating requirement of fuel cell system carries out real-time hydrogen supply.
At present, the hydrogen supply mode of Proton Exchange Membrane Fuel Cells mainly contains high-pressure hydrogen storing, metal alloy storage hydrogen, reformation hydrogen production etc.High-pressure hydrogen storing refer to more than hydrogen critical temperature by the mode of high pressure compressed by hydrogen storage in withstand voltage container.The advantage of this hydrogen supplying method be hydrogen-storing device structure simple, portably use conveniently, to fill hydrogen discharging speed fast, its weak point is that hydrogen-storage density is low, even if storage hydrogen pressure is increased to 70MPa, its volume hydrogen-storage density also only has about 4kg/100L.In addition, the transport of high-pressure hydrogen storage and use have serious potential safety hazard.Metal alloy storage hydrogen is that hydrogen is stored in metal tin with the form of metal hydride, and the heat provided by the external world realizes the release supply of hydrogen.This technology has the features such as security is high, good reliability, and its weak point is that hydrogen-storing device volume weight is large, manufacturing cost is high, hydrogen-storage density is low.The hydrogen storage alloy being in sizable application is at present TiFe alloy, and its quality hydrogen-storage density is about 1.8wt%, is difficult to the hydrogen supply demand meeting high-power Proton Exchange Membrane Fuel Cells, and mobile and transport difficult.Reformation hydrogen production refers to that the hydrogen-rich fuels such as Sweet natural gas, methyl alcohol, ethanol are under certain temperature and pressure condition, Reforming catalyst reaction occurs under the effect of catalyzer, is converted into the process of H2 and CO2.The principal feature of this technology is that device for producing hydrogen volume weight is little, hydrogen-storage density is high, structure is simple, and its weak point is to contain the foreign gases such as CO, CO2 in produced H2, needs further separation and purification before using.And conventional purification technique is pressure swing adsorption, this technology can obtain the hydrogen of higher degree, but the volume weight of pressure-swing absorption apparatus entirety is large, purification efficiency is low, and power consumption is larger, significantly reduce the generating efficiency of fuel cell system entirety, be thus not suitable for mating with fuel cell generation using.
Summary of the invention
An object of the present invention is the deficiency overcoming the online the method for hydrogen production of existing fuel cell, and provide a kind of online high-purity hydrogen preparation system for Proton Exchange Membrane Fuel Cells, it has good novelty and novelty.
The technical solution adopted for the present invention to solve the technical problems is: a kind of online high-purity hydrogen preparation system for fuel cell, the material box comprising methanol tank and be connected with methanol tank by methyl alcohol volume pump and catalytic burner, material box is provided with fuel cell and discharges water inlet, catalytic burner is provided with oxygen intake, material box is connected with alcohol water volume pump and interchanger in turn, interchanger is connected with vaporizer, vaporizer is connected with reforming reactor, reforming reactor is connected with palladium film purifier, palladium film purifier is connected with catalytic burner.
Described a kind of online high-purity hydrogen preparation system for fuel cell, its palladium film purifier is also connected with switch-valve, CO concentration sensor, pressure transmitter, temperature sensor and mass flow controller in turn.
Described a kind of online high-purity hydrogen preparation system for fuel cell, is connected with switch-valve and mass flow controller in turn between its alcohol water volume pump and interchanger.
Described a kind of online high-purity hydrogen preparation system for fuel cell, is also connected with switch-valve and mass flow controller in turn between its methyl alcohol volume pump and material box, is connected with variable valve between described methyl alcohol volume pump and catalytic burner.
Described a kind of online high-purity hydrogen preparation system for fuel cell, its methanol tank, methyl alcohol volume pump, material box, catalytic burner, alcohol water volume pump, interchanger, vaporizer and palladium film purifier are connected by stainless steel pipeline, and described pipeline is coated with thermal insulation layer.
Described a kind of online high-purity hydrogen preparation system for fuel cell, its interchanger is tube and shell heat exchanger, and described reforming reactor is the isothermal reactor or the adiabatic reactor that are provided with temperature sensor, pressure transmitter and safety valve.
Described a kind of online high-purity hydrogen preparation system for fuel cell, its palladium film purifier is the purifier of palladium-silver or palladium-copper alloy film tube bank composition, and palladium film purifier is provided with temperature sensor and pressure transmitter.
Described a kind of online high-purity hydrogen preparation system for fuel cell, its catalytic burner is adopt alumina load platinum or gold as the diffusion type flameless catalytic combustion device of catalyzer, and catalytic burner is provided with temperature sensor.
Described a kind of online high-purity hydrogen preparation system for fuel cell, its material box is provided with liquid level sensor, described methanol tank is provided with liquid level sensor.
Two of object of the present invention is the control method providing above-mentioned online high-purity hydrogen preparation system.
The technical solution adopted for the present invention to solve the technical problems is: a kind of control method of the online high-purity hydrogen preparation system for fuel cell, comprises the steps:
A) after each device element, in confirmation system is intact, open methyl alcohol volume pump, switch-valve and variable valve, pass into the catalyticcombustion that oxygen carries out methyl alcohol simultaneously, after the temperature in palladium film purifier and reforming reactor rises to 400 DEG C, open alcohol water volume pump and switch-valve, regulated the flow of alcohol-water mixture by alcohol water volume pump;
B), alcohol-water mixture is converted into high-temperature gas mixture after interchanger heat exchange, vaporizer heating, and carry out Reforming catalyst reaction in reforming reactor, online hydrogen generating system has started;
C), close variable valve after online hydrogen generating system normal operation, burning reformate tail gas carries out catalyticcombustion heat supply, opens switch-valve to fuel cell supply of hydrogen simultaneously;
D), by carbon monoxide concentration sensor, pressure transmitter, the carbon monoxide content of the pure hydrogen of temperature sensor Real-Time Monitoring, pure hydrogen pressure, temperature, control by regulating the flow of flow to pure hydrogen of alcohol-water mixture.
Beneficial effect of the present invention is:
System carries out online hydrogen supply in the mode of methanol-water reforming reaction hydrogen manufacturing, pure hydrogen output controls by regulating the flow of alcohol-water mixture, the method has that hydrogen-storage density is large, hydrogen purity is high, energy consumption is low, compact construction, on off control are easy, is easy to realize the features such as modular design, and can realize start & shutdown through one key.
Heat required for system starts is provided by the catalyticcombustion of methyl alcohol, after hydrogen generating system operates steadily, the catalyticcombustion that institute's heat requirement is separated reformate gas gained tail gas by palladium film purifier provides, the high-temperature gas that methyl alcohol or the tail gas catalyzed burning of reforming reaction produce successively flows through palladium film purifier, reforming reactor, vaporizer, discharge after carrying out heat exchange finally by interchanger and alcohol-water mixture, because system start-up and operation time institute heat requirement comes from the catalyticcombustion of methyl alcohol and reforming reaction tail gas respectively, reduce the energy consumption consumption of system and the requirement of subsidiary conditions to external world.
Accompanying drawing explanation
Fig. 1 is system architecture schematic diagram of the present invention.
Each Reference numeral is: 1-material box, 1.1-liquid level sensor, 2-alcohol water volume pump, 2.1-switch-valve, 2.2-mass flow controller, 3-interchanger, 4-vaporizer, 5-reforming reactor, 5.1-pressure transmitter, 5.2-temperature sensor, 5.3-safety valve, 6-palladium film purifier, 6.1-temperature sensor, 6.2-pressure transmitter, 6.3-switch-valve, 6.4-CO concentration sensor, 6.5-pressure transmitter, 6.6-temperature sensor, 6.7-mass flow controller, 7-catalytic burner, 7.1-temperature sensor, 8-methanol tank, 8.1-liquid level sensor, 9.1-mass flow controller, 9.2-switch-valve, 9.3-variable valve, 10-oxygen intake, water inlet discharged by 11-fuel cell.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
With reference to shown in Fig. 1, the invention discloses a kind of online high-purity hydrogen preparation system for fuel cell, the material box 1 comprising methanol tank 8 and be connected with methanol tank 8 by methyl alcohol volume pump 9 and catalytic burner 7, flow of methanol is divided into two branch roads to be delivered to material box 1 and catalytic burner 7 respectively after methyl alcohol volume pump 9, switch-valve 9.2 and mass flow controller 9.1 is also connected with in turn between described methyl alcohol volume pump 9 and material box 1, variable valve 9.3 is connected with between described methyl alcohol volume pump 9 and catalytic burner 7, the flow of methyl alcohol is by methyl alcohol volume pump 9, mass flow controller 9.1, switch-valve 9.2 and variable valve 9.3 carry out regulating and controlling, material box 1 is provided with fuel cell and discharges water inlet 11, to be collected by pipeline for water that fuel cell operation is produced and be delivered in material box 1, described material box 1 is provided with liquid level sensor 1.1, described methanol tank 8 is provided with liquid level sensor 8.1, described catalytic burner 7 is adopt alumina load platinum or gold as the diffusion type flameless catalytic combustion device of catalyzer, catalytic burner 7 is provided with temperature sensor 7.1, catalytic burner 7 is provided with oxygen intake 10, the catalyticcombustion of methyl alcohol is completed for passing into oxygen, material box 1 is connected with alcohol water volume pump 2 and interchanger 3 in turn, after first alcohol and water presses the volume ratio mixing of 1:1-1:2, export by alcohol water volume pump 2 high-temperature gas produced in interchanger 3 and catalytic burner 7 to and carry out heat exchange, described interchanger 3 is tube and shell heat exchanger, alcohol-water mixture flows through shell side, high-temperature gas flows through tube side, switch-valve 2.1 and mass flow controller 2.2 is connected with in turn between alcohol water volume pump 2 and interchanger 3, the flow of alcohol-water mixture is by alcohol water volume pump 2, switch-valve 2.1 and mass flow controller 2.2 carry out regulating and controlling, interchanger 3 is connected with vaporizer 4, be heated to be high-temperature gas mixture further, vaporizer 4 is connected with reforming reactor 5, Reforming catalyst is carried out to mixed gas and has reacted online hydrogen manufacturing, described reforming reactor 5 is for being provided with temperature sensor 5.2, the isothermal reactor of pressure transmitter 5.1 and safety valve 5.3 or adiabatic reactor, reforming reactor 5 is connected with palladium film purifier 6, purifying is carried out to the thick hydrogen of reformation catalyzed reaction gained, described palladium film purifier 6 is the purifier of palladium-silver or palladium-copper alloy film tube bank composition, bundled tube palladium film purifier 6 is provided with temperature sensor 6.1 and pressure transmitter 6.2, palladium film purifier 6 is connected with catalytic burner 7, complete the burning of Reforming catalyst reaction end gas, hydrogen delivery conduit after purifying is disposed with switch-valve 6.3, CO concentration sensor 6.4, pressure transmitter 6.5, temperature sensor 6.6 and mass flow controller 6.7, for the carbon monoxide content of the pure hydrogen of Real-Time Monitoring, pressure and temperature, described methanol tank 8, methyl alcohol volume pump 9, material box 1, catalytic burner 7, alcohol water volume pump 2, interchanger 3, vaporizer 4 and palladium film purifier 6 are by corrosion-resistant, 304 or 316 stainless steel pipelines of resistance to hydrogen embrittlement are connected, described pipeline is coated with the thermal insulation layer of silicates inorganic materials, described liquid level sensor 1.1, liquid level sensor 8.1, mass flow controller 2.2, mass flow controller 6.7, mass flow controller 9.1, temperature sensor 5.2, temperature sensor 6.1, temperature sensor 6.6, temperature sensor 7.1 and pressure transmitter 5.1, pressure transmitter 6.2, pressure transmitter 6.5, CO concentration sensor 6.4 monitors the liquid level of its installation place, place in real time, mass rate, temperature, pressure, the operating parameters such as carbon monoxide concentration are also fed back with 4-20mA input/output signal.
For a control method for the online high-purity hydrogen preparation system of fuel cell, comprise the steps:
A) after each device element, in confirmation system is intact, open methyl alcohol volume pump 9, switch-valve 9.2 and variable valve 9.3, pass into the catalyticcombustion that oxygen carries out methyl alcohol simultaneously, after the temperature in palladium film purifier 6 and reforming reactor 5 rises to 400 DEG C, open alcohol water volume pump 2 and switch-valve 2.1, regulated the flow of alcohol-water mixture by alcohol water volume pump 2;
B), alcohol-water mixture is converted into high-temperature gas mixture through interchanger 3 heat exchange, vaporizer 4 after heating, and carry out Reforming catalyst reaction in reforming reactor 5, online hydrogen generating system has started;
C) pressure in purifier 6, is monitored, when pressure is 1.0MPa, methyl alcohol supply branch road valve---the variable valve 9.3 passing into catalytic burner 7 is closed after showing online hydrogen generating system normal operation, burning reformate tail gas carries out catalyticcombustion heat supply, and open the supply of pure hydrogen valve---switch-valve 6.3 is to fuel cell supply of hydrogen simultaneously;
D), by carbon monoxide concentration sensor 6.4, pressure transmitter 6.2, the carbon monoxide content of the pure hydrogen of temperature sensor 6.6 Real-Time Monitoring, pure hydrogen pressure, temperature, control by regulating the flow of flow to pure hydrogen of alcohol-water mixture.
Online hydrogen generating system provided by the invention has that hydrogen-storage density is large, hydrogen purity is high, energy consumption is low, compact construction, on off control are easy, is easy to realize the features such as modular design.The sensor of Operation system setting is used for monitoring and Real-time Feedback signal, and online hydrogen production reaction can realize start & shutdown through one key.
Above-described embodiment is illustrative principle of the present invention and effect thereof only; and the embodiment that part is used, for the person of ordinary skill of the art, without departing from the concept of the premise of the invention; can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (10)
1. the online high-purity hydrogen preparation system for fuel cell, it is characterized in that: comprise methanol tank (8) and the material box (1) that is connected with methanol tank (8) by methyl alcohol volume pump (9) and catalytic burner (7), material box (1) is provided with fuel cell and discharges water inlet (11), catalytic burner (7) is provided with oxygen intake (10), material box (1) is connected with alcohol water volume pump (2) and interchanger (3) in turn, interchanger (3) is connected with vaporizer (4), vaporizer (4) is connected with reforming reactor (5), reforming reactor (5) is connected with palladium film purifier (6), palladium film purifier (6) is connected with catalytic burner (7).
2. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 1, it is characterized in that, described palladium film purifier (6) is also connected with switch-valve (6.3), CO concentration sensor (6.4), pressure transmitter (6.5), temperature sensor (6.6) and mass flow controller (6.7) in turn.
3. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 1, is characterized in that, be connected with switch-valve (2.1) and mass flow controller (2.2) between described alcohol water volume pump (2) and interchanger (3) in turn.
4. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 1, it is characterized in that, also be connected with switch-valve (9.2) and mass flow controller (9.1) between described methyl alcohol volume pump (9) and material box (1) in turn, between described methyl alcohol volume pump (9) and catalytic burner (7), be connected with variable valve (9.3).
5. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 1 or 2 or 3 or 4, it is characterized in that, described methanol tank (8), methyl alcohol volume pump (9), material box (1), catalytic burner (7), alcohol water volume pump (2), interchanger (3), vaporizer (4) and palladium film purifier (6) are connected by stainless steel pipeline, and described pipeline is coated with thermal insulation layer.
6. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 5, it is characterized in that, described interchanger (3) is tube and shell heat exchanger, and described reforming reactor (5) is for being provided with isothermal reactor or the adiabatic reactor of temperature sensor (5.2), pressure transmitter (5.1) and safety valve (5.3).
7. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 6, it is characterized in that, the purifier that described palladium film purifier (6) forms for palladium-silver or the tube bank of palladium-copper alloy film, palladium film purifier (6) is provided with temperature sensor (6.1) and pressure transmitter (6.2).
8. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 7, it is characterized in that, described catalytic burner (7), for adopting alumina load platinum or gold as the diffusion type flameless catalytic combustion device of catalyzer, catalytic burner (7) is provided with temperature sensor (7.1).
9. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 8, is characterized in that, described material box (1) is provided with liquid level sensor (1.1), described methanol tank (8) is provided with liquid level sensor (8.1).
10. as described in claim 4 to 9 any one for a control method for the online high-purity hydrogen preparation system of fuel cell, it is characterized in that, comprise the steps:
A) after each device element, in confirmation system is intact, open methyl alcohol volume pump (9), switch-valve (9.2) and variable valve (9.3), pass into the catalyticcombustion that oxygen carries out methyl alcohol simultaneously, after the temperature in palladium film purifier (6) and reforming reactor (5) rises to 400 DEG C, open alcohol water volume pump (2) and switch-valve (2.1), regulated the flow of alcohol-water mixture by alcohol water volume pump (2);
B), alcohol-water mixture is converted into high-temperature gas mixture after interchanger (3) heat exchange, vaporizer (4) heating, and carry out Reforming catalyst reaction in reforming reactor (5), online hydrogen generating system has started;
C), close variable valve (9.3) after online hydrogen generating system normal operation, burning reformate tail gas carries out catalyticcombustion heat supply, opens switch-valve (6.3) to fuel cell supply of hydrogen simultaneously;
D), by carbon monoxide content, pure hydrogen pressure, the temperature of carbon monoxide concentration sensor (6.4), pressure transmitter (6.2), the pure hydrogen of temperature sensor (6.6) Real-Time Monitoring, control by regulating the flow of flow to pure hydrogen of alcohol-water mixture.
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