CN105152133B - A kind of online high-purity hydrogen preparation system and its control method for fuel cell - Google Patents

A kind of online high-purity hydrogen preparation system and its control method for fuel cell Download PDF

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CN105152133B
CN105152133B CN201510558853.1A CN201510558853A CN105152133B CN 105152133 B CN105152133 B CN 105152133B CN 201510558853 A CN201510558853 A CN 201510558853A CN 105152133 B CN105152133 B CN 105152133B
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hydrogen
fuel cell
online
methanol
measuring pump
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CN105152133A (en
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吴飞
范晶
张聪
周晶晶
管道安
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HUBEI GREATSEA NEWPOWER TECHNOLOGY Co Ltd
No712 Inst China Ship Heavy Industry Group Co
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HUBEI GREATSEA NEWPOWER TECHNOLOGY Co Ltd
No712 Inst China Ship Heavy Industry Group Co
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

The invention discloses a kind of online high-purity hydrogen preparation system for fuel cell, the material box and catalytic burner being connected including methanol tank and by methanol measuring pump with methanol tank, material box discharges water inlet provided with fuel cell, catalytic burner is provided with oxygen intake, it is connected with alcohol water measuring pump and heat exchanger on material box in turn, vaporizer is connected with heat exchanger, reforming reactor is connected with vaporizer, palladium film purifier is connected with reforming reactor, palladium film purifier is connected with catalytic burner;Also disclose the control method of said system.Present system carries out online hydrogen supply in the way of methanol-water reforming reaction hydrogen manufacturing, pure hydrogen yield is controlled by adjusting the flow of alcohol-water mixture, and this method has that hydrogen-storage density is big, hydrogen purity is high, energy consumption is low, compact conformation, start-up and shut-down control are easy, the features such as be easily achieved modularized design.

Description

A kind of online high-purity hydrogen preparation system and its control method for fuel cell
Technical field
The invention belongs to online hydrogen producing technology field, it is related to a kind of online hydrogen manufacturing system for Proton Exchange Membrane Fuel Cells System, and its control method.
Background technology
Fuel cell is a kind of efficient generating apparatus without combustion process.Fuel cell and traditional battery Difference, it is directly by the chemical energy being stored in fuel and oxidant by being electrochemically converted into electric energy.Fuel cell has Many types, can be divided into by the difference of electrolyte:Alkaline fuel cell, phosphoric acid type fuel cell, molten carbonate fuel cell, Proton Exchange Membrane Fuel Cells and SOFC etc..Wherein, Proton Exchange Membrane Fuel Cells and other kinds of Fuel cell is compared, excellent with high power density, high-energy conversion efficiency, low-vibration noise, cold-starting, environment-friendly etc. Point.At present, Proton Exchange Membrane Fuel Cells is widely used to clean energy resource, traffic, distributed power station, emergency power supply, national defence The fields such as military project.
High-purity hydrogen is the fuel of Proton Exchange Membrane Fuel Cells.The method of industrial prepare with scale high-purity hydrogen is main For water electrolysis hydrogen producing, hydrogen making by natural gas reformation etc..When Proton Exchange Membrane Fuel Cells is as electricity generation system, high-purity hydrogen is generally deposited It is stored in specific device, and the service requirement of fuel cell system carries out real-time hydrogen supply.
At present, the hydrogen supply mode of Proton Exchange Membrane Fuel Cells mainly has high-pressure hydrogen storing, metal alloy hydrogen storage, reformation hydrogen production Deng.High-pressure hydrogen storing refer to hydrogen critical-temperature above by the mode of high pressure compressed by hydrogen storage in pressure-resistant container. The advantage of the hydrogen supplying method is that hydrogen-storing device is simple in construction, it is easy to use to carry, fills hydrogen discharging speed soon, and it is disadvantageous in that storage Hydrogen density is low, even if hydrogen storage pressure is improved to 70MPa, and its volume hydrogen-storage density also only has 4kg/100L or so.In addition, high pressure The transport and use of hydrogen storage vessel have serious potential safety hazard.Metal alloy hydrogen storage is that hydrogen is stored up in the form of metal hydride It is stored in metal can, the heat provided by the external world realizes that the release of hydrogen is supplied.The technology has safe, good reliability The features such as, it is disadvantageous in that hydrogen-storing device volume weight is big, manufacturing cost is high, hydrogen-storage density is low.Being currently in scale should Hydrogen bearing alloy is TiFe alloys, and its quality hydrogen-storage density is about 1.8wt%, it is difficult to meet high-power pem fuel The hydrogen supply demand of battery, and mobile and transport difficult.Reformation hydrogen production refers to the hydrogen-rich fuels such as natural gas, methanol, ethanol certain Under the conditions of temperature and pressure, Reforming catalyst reaction occurs in the presence of catalyst, H2 and CO2 process is converted into.The technology Be mainly characterized by that device for producing hydrogen volume weight is small, hydrogen-storage density is high, simple in construction, it is disadvantageous in that produced H2 In containing the foreign gas such as CO, CO2, need further to isolate and purify before use.And conventional purification technique is pressure-variable adsorption skill Art, the technology can obtain the hydrogen of higher degree, but the overall volume weight of pressure-swing absorption apparatus is big, and purification efficiency is low, And power consumption is larger, the overall generating efficiency of fuel cell system is significantly reduced, thus is not suitable for and fuel cell power generation System matches are used.
The content of the invention
An object of the present invention is to overcome the shortcomings of that the online the method for hydrogen production of existing fuel cell is used for matter there is provided one kind The online high-purity hydrogen preparation system of proton exchange film fuel cell, it has preferable novelty and novelty.
The technical solution adopted for the present invention to solve the technical problems is:A kind of online high-purity hydrogen for fuel cell Preparation system, including methanol tank and the material box and catalytic burner that are connected by methanol measuring pump with methanol tank, material box Water inlet is discharged provided with fuel cell, catalytic burner, which is provided with oxygen intake, material box, is connected with the metering of alcohol water in turn It is connected with pump and heat exchanger, heat exchanger on vaporizer, vaporizer and is connected with reforming reactor, palladium is connected with reforming reactor Film purifier, palladium film purifier is connected with catalytic burner.
Also it is sequentially connected on a kind of described online high-purity hydrogen preparation system for fuel cell, its palladium film purifier There are switch valve, CO concentration sensors, pressure sensor, temperature sensor and mass flow controller.
Described a kind of online high-purity hydrogen preparation system for fuel cell, between its alcohol water measuring pump and heat exchanger It is connected with switch valve and mass flow controller in turn.
Described a kind of online high-purity hydrogen preparation system for fuel cell, between its methanol measuring pump and material box Also it is connected with switch valve and mass flow controller in turn, regulation is connected between described methanol measuring pump and catalytic burner Valve.
A kind of described online high-purity hydrogen preparation system for fuel cell, its methanol tank, methanol measuring pump, raw material Case, catalytic burner, alcohol water measuring pump, heat exchanger, vaporizer and palladium film purifier are connected by stainless steel pipeline, Described pipeline is coated with heat-insulation layer.
A kind of described online high-purity hydrogen preparation system for fuel cell, its heat exchanger is shell-and-tube heat exchanger, Described reforming reactor is isothermal reactor or the heat-insulating reaction for being provided with temperature sensor, pressure sensor and safety valve Device.
A kind of described online high-purity hydrogen preparation system for fuel cell, its palladium film purifier is palladium-silver or palladium copper Temperature sensor and pressure sensor are provided with the purifier of alloy membrane tube bundle composition, palladium film purifier.
A kind of described online high-purity hydrogen preparation system for fuel cell, its catalytic burner is to use aluminum oxide Temperature sensor is provided with Supported Pt Nanoparticles or the golden diffusion type flameless catalytic combustion device as catalyst, catalytic burner.
Level sensing is provided with a kind of described online high-purity hydrogen preparation system for fuel cell, its material box Liquid level sensor is provided with device, described methanol tank.
The second object of the present invention is the control method for 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 online high-purity hydrogen for fuel cell The control method of preparation system, comprises the following steps:
a), each device element in confirmation system it is intact after, open methanol measuring pump, switch valve and regulating valve, lead to simultaneously Enter the catalysis burning that oxygen carries out methanol, after the temperature in palladium film purifier and reforming reactor rises to 400 DEG C, open alcohol water Measuring pump and switch valve, the flow of alcohol-water mixture is adjusted by alcohol water measuring pump;
b), alcohol-water mixture exchanges heat through heat exchanger, high-temperature gas mixture is converted into after vaporizer heating, and in reforming reactor Middle progress Reforming catalyst reaction, online hydrogen generating system start completion;
c), close regulating valve after line hydrogen generating system normal operation, burning reformate tail gas carries out catalysis combustion heat supplying, Switch valve is opened simultaneously supplies hydrogen to fuel cell;
d), monitor by carbonomonoxide concentration sensor, pressure sensor, temperature sensor the carbon monoxide of pure hydrogen in real time Content, pure hydrogen pressure, temperature, are controlled by the flow for adjusting alcohol-water mixture to the flow of pure hydrogen.
The beneficial effects of the present invention are:
System carries out online hydrogen supply in the way of methanol-water reforming reaction hydrogen manufacturing, and pure hydrogen yield is by adjusting alcohol-water mixture Flow be controlled, this method has that hydrogen-storage density is big, hydrogen purity is high, energy consumption is low, compact conformation, start-up and shut-down control are easy, The features such as being easily achieved modularized design, and start & shutdown through one key can be realized.
Heat required for system starts is provided by the catalysis burning of methanol, after hydrogen generating system operates steadily, institute's calorific requirement The catalysis of tail gas as obtained by palladium film purifier separates reformate gas, which is burnt, to be provided, methanol or the tail gas catalyzed burning of reforming reaction The high-temperature gas of generation successively flows through palladium film purifier, reforming reactor, vaporizer, finally by heat exchanger and alcohol-water mixture Discharged after heat exchange, urging for methanol and reforming reaction tail gas is respectively from by system starts and run when institute's calorific requirement Change burning, reduce the energy consumption consumption and the requirement of subsidiary conditions to external world of system.
Brief description of the drawings
Fig. 1 is system structure diagram of the invention.
Each reference is:1- material boxes, 1.1- liquid level sensors, 2- alcohol water measuring pumps, 2.1-switch valve, 2.2-mass flow controller, 3-heat exchanger, 4-vaporizer, 5-reforming reactor, 5.1-pressure sensor, 5.2-temperature Spend sensor, 5.3-safety valve, 6-palladium film purifier, 6.1-temperature sensor, 6.2-pressure sensor, 6.3-switch Valve, 6.4-CO concentration sensors, 6.5-pressure sensor, 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-regulating valve, 10-oxygen intake, 11-fuel cell discharge water inlet.
Embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
Shown in reference picture 1, the invention discloses a kind of online high-purity hydrogen preparation system for fuel cell, including first Alcohol case 8 and the material box 1 and catalytic burner 7 being connected by methanol measuring pump 9 with methanol tank 8, methanol flow through methanol metering Be divided into two branch roads after pump 9 and be delivered to material box 1 and catalytic burner 7 respectively, described methanol measuring pump 9 and material box 1 it Between be also connected with switch valve 9.2 and mass flow controller 9.1 in turn, between described methanol measuring pump 9 and catalytic burner 7 Regulating valve 9.3 is connected with, the flow of methanol passes through methanol measuring pump 9, mass flow controller 9.1, switch valve 9.2 and regulation Valve 9.3 is controlled regulation, and material box 1 discharges water inlet 11 provided with fuel cell, for by produced by fuel cell operation Water collect and be delivered in material box 1 by pipeline, liquid level sensor 1.1, described first are provided with described material box 1 Liquid level sensor 8.1 is provided with alcohol case 8, described catalytic burner 7 is to be used as catalyst using alumina load platinum or gold Diffusion type flameless catalytic combustion device, temperature sensor 7.1 is provided with catalytic burner 7, catalytic burner 7 is provided with oxygen Entrance 10, completes to be connected with alcohol water measuring pump 2 and heat exchanger in turn on the catalysis burning of methanol, material box 1 for being passed through oxygen 3, first alcohol and water presses 1:1—1:After 2 volume ratio mixing, exported by alcohol water measuring pump 2 to heat exchanger 3 and catalytic burner 7 The high-temperature gas of middle generation carries out heat exchange, and described heat exchanger 3 is shell-and-tube heat exchanger, and alcohol-water mixture flows through shell side, high Wet body flows through tube side, and switch valve 2.1 and mass flow controller are connected with turn between alcohol water measuring pump 2 and heat exchanger 3 2.2, the flow of alcohol-water mixture is controlled tune by alcohol water measuring pump 2, switch valve 2.1 and mass flow controller 2.2 Vaporizer 4 is connected with section, heat exchanger 3, is further heated to be on high-temperature gas mixture, vaporizer 4 and is connected with reforming reactor 5, Reforming catalyst reaction is carried out to mixed gas and completes online hydrogen manufacturing, described reforming reactor 5 is to be provided with temperature sensor 5.2nd, palladium is connected with the isothermal reactor or adiabatic reactor of pressure sensor 5.1 and safety valve 5.3, reforming reactor 5 Film purifier 6, is purified, described palladium film purifier 6 is palladium-silver or palladium-copper alloy film to reforming thick hydrogen obtained by catalytic reaction Restrain and be provided with temperature sensor 6.1 and pressure sensor 6.2 on the purifier of composition, bundled tube palladium film purifier 6, palladium film is pure Change device 6 to be connected with catalytic burner 7, complete on the burning of Reforming catalyst reaction end gas, hydrogen output pipe after purification successively It is provided with switch valve 6.3, CO concentration sensors 6.4, pressure sensor 6.5, temperature sensor 6.6 and mass flow controller 6.7, carbon monoxide content, pressure and temperature for monitoring pure hydrogen in real time, described methanol tank 8, methanol measuring pump 9, raw material Case 1, catalytic burner 7, alcohol water measuring pump 2, heat exchanger 3, vaporizer 4 and palladium film purifier 6 pass through corrosion-resistant, resistance to hydrogen embrittlement 304 or 316 stainless steel pipelines are connected, and described pipeline is coated with the heat-insulation layer of silicates inorganic material, described Liquid level sensor 1.1, liquid level sensor 8.1, mass flow controller 2.2, mass flow controller 6.7, mass flow control Device 9.1 processed, temperature sensor 5.2, temperature sensor 6.1, temperature sensor 6.6, temperature sensor 7.1 and pressure sensor 5.1st, liquid level, the matter of installation place where pressure sensor 6.2, pressure sensor 6.5, CO concentration sensors 6.4 monitor it in real time The operational factors such as amount flow, temperature, pressure, carbonomonoxide concentration are simultaneously fed back with 4-20mA input/output signals.
A kind of control method of online high-purity hydrogen preparation system for fuel cell, comprises the following steps:
a), each device element in confirmation system it is intact after, open methanol measuring pump 9, switch valve 9.2 and regulating valve 9.3, The catalysis burning that oxygen carries out methanol is passed through simultaneously, after the temperature in palladium film purifier 6 and reforming reactor 5 rises to 400 DEG C, Alcohol water measuring pump 2 and switch valve 2.1 are opened, the flow of alcohol-water mixture is adjusted by alcohol water measuring pump 2;
b), alcohol-water mixture exchanges heat through heat exchanger 3, vaporizer 4 is converted into high-temperature gas mixture after heating, and in reforming reaction Reforming catalyst reaction, online hydrogen generating system start completion are carried out in device 5;
c), monitoring purifier 6 in pressure, when pressure be 1.0MPa when, show after line hydrogen generating system normal operation close Methanol supply branch road valve --- the regulating valve 9.3 for being passed through catalytic burner 7 is closed, burning reformate tail gas carries out catalysis burning Heat supply, while opening pure hydrogen supply valve door --- switch valve 6.3 supplies hydrogen to fuel cell;
d), pure hydrogen monitored by carbonomonoxide concentration sensor 6.4, pressure sensor 6.2, temperature sensor 6.6 in real time Carbon monoxide content, pure hydrogen pressure, temperature, the flow of pure hydrogen is controlled by the flow for adjusting alcohol-water mixture.
The online hydrogen generating system that the present invention is provided has that hydrogen-storage density is big, hydrogen purity is high, energy consumption is low, compact conformation, open The features such as stopping control simplicity, be easily achieved modularized design.The sensor that system is set is used to monitor and Real-time Feedback signal, Line hydrogen production reaction can realize start & shutdown through one key.
The above-described embodiments merely illustrate the principles and effects of the present invention, and the embodiment that part is used, for For one of ordinary skill in the art, without departing from the concept of the premise of the invention, can also make it is some deformation and Improve, these belong to protection scope of the present invention.

Claims (10)

1. a kind of online high-purity hydrogen preparation system for fuel cell, it is characterised in that:Including methanol tank(8)And pass through Methanol measuring pump(9)With methanol tank(8)The material box of connection(1)And catalytic burner(7), material box(1)Provided with fuel electricity Discharge water inlet in pond(11), catalytic burner(7)It is provided with oxygen intake(10), material box(1)On be connected with alcohol water meter in turn Measure pump(2)And heat exchanger(3), heat exchanger(3)On be connected with vaporizer(4), vaporizer(4)On be connected with reforming reactor(5), Reforming reactor(5)On be connected with palladium film purifier(6), palladium film purifier(6)With catalytic burner(7)Connection.
2. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 1, it is characterised in that institute The palladium film purifier stated(6)On be also connected with switch valve in turn(6.3), CO concentration sensors(6.4), pressure sensor(6.5)、 Temperature sensor(6.6)And mass flow controller(6.7).
3. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 1, it is characterised in that institute The alcohol water measuring pump stated(2)And heat exchanger(3)Between be connected with switch valve in turn(2.1)And mass flow controller(2.2).
4. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 1, it is characterised in that institute The methanol measuring pump stated(9)And material box(1)Between be also connected with switch valve in turn(9.2)And mass flow controller(9.1), Described methanol measuring pump(9)And catalytic burner(7)Between be connected with regulating 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 special Levy and be, described methanol tank(8), methanol measuring pump(9), material box(1), catalytic burner(7), alcohol water measuring pump(2), change Hot device(3), vaporizer(4)And palladium film purifier(6)It is connected by stainless steel pipeline, described pipeline is coated with Heat-insulation layer.
6. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 5, it is characterised in that institute The heat exchanger stated(3)For shell-and-tube heat exchanger, described reforming reactor(5)To be provided with temperature sensor(5.2), pressure pass Sensor(5.1)And safety valve(5.3)Isothermal reactor or adiabatic reactor.
7. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 6, it is characterised in that institute The palladium film purifier stated(6)The purifier constituted for palladium-silver or palladium-copper alloy membrane tube bundle, palladium film purifier(6)On be provided with temperature Sensor(6.1)And pressure sensor(6.2).
8. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 7, it is characterised in that institute The catalytic burner stated(7)To be used as the diffusion type flameless catalytic combustion device of catalyst, catalysis using alumina load platinum or gold Burner(7)On be provided with temperature sensor(7.1).
9. a kind of online high-purity hydrogen preparation system for fuel cell according to claim 8, it is characterised in that institute The material box stated(1)On be provided with liquid level sensor(1.1), described methanol tank(8)On be provided with liquid level sensor(8.1).
10. a kind of control for the online high-purity hydrogen preparation system for being used for fuel cell as described in claim 4 to 9 any one Method, it is characterised in that comprise the following steps:
a), each device element in confirmation system it is intact after, open methanol measuring pump(9), switch valve(9.2)And regulating valve (9.3), while being passed through the catalysis burning that oxygen carries out methanol, treat palladium film purifier(6)And reforming reactor(5)In temperature liter To after 400 DEG C, alcohol water measuring pump is opened(2)And switch valve(2.1), pass through alcohol water measuring pump(2)Adjust the stream of alcohol-water mixture Amount;
b), alcohol-water mixture is through heat exchanger(3)Heat exchange, vaporizer(4)High-temperature gas mixture is converted into after heating, and in reforming reaction Device(5)Middle progress Reforming catalyst reaction, online hydrogen generating system start completion;
c), after line hydrogen generating system normal operation close regulating valve(9.3), the progress catalysis burning confession of burning reformate tail gas Heat, while opening switch valve(6.3)Hydrogen is supplied to fuel cell;
d), pass through carbonomonoxide concentration sensor(6.4), pressure sensor(6.2), temperature sensor(6.6)Monitor in real time pure The carbon monoxide content of hydrogen, pure hydrogen pressure, temperature, are controlled by the flow for adjusting alcohol-water mixture to the flow of pure hydrogen.
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CN105655615A (en) * 2016-04-07 2016-06-08 北京建筑大学 Methanol fuel battery system for automobile and working method of system
CN106379337A (en) * 2016-11-02 2017-02-08 上海钧希新能源科技有限公司 Methanol supply system based on methanol air conditioner of rail train
JP6801790B2 (en) * 2017-07-28 2020-12-16 日産自動車株式会社 Fuel cell system and its control method
CN111628190A (en) * 2019-02-27 2020-09-04 国家能源投资集团有限责任公司 Fuel cell system
CN111048809A (en) * 2019-12-13 2020-04-21 沈阳航空航天大学 Hydrogen-oxygen fuel cell intelligent power generation system based on hydrogen production by straw ethanol fermentation and reforming
CN111864232A (en) * 2020-08-03 2020-10-30 上海重塑能源科技有限公司 Gas purity detection method and hydrogen purity detection device of hydrogen supply system

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