CN105720285B - A kind of closed-type fuel cell hydrogen source system - Google Patents
A kind of closed-type fuel cell hydrogen source system Download PDFInfo
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- CN105720285B CN105720285B CN201410741183.2A CN201410741183A CN105720285B CN 105720285 B CN105720285 B CN 105720285B CN 201410741183 A CN201410741183 A CN 201410741183A CN 105720285 B CN105720285 B CN 105720285B
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
Abstract
A kind of closed-type fuel cell hydrogen source system, including methanol feeding mechanism, liquid oxygen apparatus, carbon dioxide storage device, water storage device, conduction oil stocking system and hydrogen production units by carbinol system；Wherein: including combustion evaporator processed, reformer, burner, carbon monoxide selective oxidizing reaction device and other auxiliary systems in hydrogen production units by carbinol；Burner, reformer, evaporator and CO selective oxidation reaction device general module；The methanol feeding mechanism, liquid oxygen apparatus are connected to the entrance of hydrogen production units by carbinol；Conduction oil stocking system is connected to the entrance and exit of hydrogen production units by carbinol；Carbon dioxide storage device, liquid water storage device are connected to the entrance and exit of hydrogen from methyl alcohol respectively.Advantages of the present invention: the closed operation of total system is realized.The consumption for saving methanol fuel, further improves the energy utilization of whole system, hydrogen production system employing reforming technology it is compact-sized.
Description
Technical field
The present invention relates to closed hydrocarbon fuels reformation hydrogen production field, in particular to a kind of enclosed fuel electricity
Pond hydrogen source system.
Background technique
The reserves of hydrogen on earth are very rich, and combustion heat value is high, and do not generate any pollution after burning, therefore are counted as 21
Century ideal clean new energy.Converting electric energy for Hydrogen Energy is Hydrogen Technology using most important aspect, and using hydrogen as fuel
Fuel cell be even more abreast of the times development.Fuel cell is a kind of using redox reaction that the chemical energy in substance is straight
Switch through the device for turning to electric energy, energy conversion efficiency is up to 50-60%.This high-energy conversion efficiency of fuel cell and
Started quickly at low temperature, low heat-emissive, low emission, running noises are low, adapt to the advantage that different capacity requires, and apply it in market
Aspect has good prospect.
In numerous kinds of fuel cells, Proton Exchange Membrane Fuel Cells (PEMFC) is due to near-zero release, starting side
Just, the features such as specific power is big, low operation temperature (50-80 DEG C), electroless mass flow are lost, water easily excludes, long service life, it is shown that
Powerful application prospect.PEMFC can not only be applied on space and military affairs, be also used as novel portable power power supply
Applied on the vehicles such as automobile.However, the fuel of PEMFC is hydrogen, since gaseous state hydrogen-feeding system is too huge and liquid
A large amount of energy can be lost in hydrogen again, be unsuitable in onboard system.Moreover, hydrogen is a kind of inflammable and explosive gas, when leakage
It is not easy to discover, therefore, PEMFC is used on a large scale, it is necessary to solve the storage, transport and safety problem of hydrogen.
Overcome the above problem a solution be at the scene that fuel cell uses, using fuel hydrogen generating system, from
The qualified hydrogen-rich that fuel cell needs are quickly prepared in the hydrocarbons such as methanol, natural gas, liquefied gas, gasoline, diesel oil is mixed
Close gas.The combined system of above-mentioned fuel hydrogen manufacturing and fuel cell is considered as commercializing fuel cells using maximally efficient side
Formula.This class A fuel A hydrogen generating system will generally pass through multiple conversion processes, can just obtain the hydrogen-rich mixed gas of fuel cell needs.
Compared with other hydrocarbons, hydrogen from methyl alcohol has apparent advantage: being liquid under methanol room temperature, transports convenience, source
It extensively, can also be by renewable biomass even municipal refuse system other than the fossil fuels such as available petroleum, natural gas and coal
It is standby；In addition, hydrogen from methyl alcohol reaction condition is mild, reforming conversion is high, be not easy carbon distribution, has very high H/C ratio, hydrogen in product
Content is high, and CO content is low etc..Therefore, methanol is considered as the desirable feedstock of fuel cell hydrogen-feeding.
In preparing hydrogen by reforming methanol reaction, mainly have Methanol cluster hydrogen manufacturing (MSR), methanol fractions oxidation catalysis is reformed
Three kinds of methods of hydrogen manufacturing (POR) and methanol nature catalytically reforming hydrogen producing (ATR), the wherein chemical reaction equation of Methanol cluster
Formula is as follows:
CH3OH+H2O→CO2+3H2ΔH298=49.5kJ/mol
From the point of view of atom economy angle, methanol steam catalytically reforming hydrogen producing is hydrogen manufacturing content highest in methanol recapitalization system
Reaction, equimolar first alcohol and water under the effect of the catalyst, generates one mole of carbon dioxide and three moles of hydrogen.First
The major advantage of alcohol steam reforming hydrogen manufacturing system is that reaction condition is mild, and hydrogen content is high in product, by-product CO concentration compared with
It is low.This is of crucial importance for providing reliable hydrogen source for PEMFC.Because the CO in hydrogen-rich reformed gas is PEMFC electrode Pt catalysis
The poisonous substance of agent, a small amount of CO can cause catalyst poisoning to reduce the activity of elctro-catalyst, lead to the decline of battery performance.
Therefore under normal circumstances, CO content therein is down to 10ppm or less by the hydrogen-rich reformed gas fuel requirement for being supplied to PEMFC.
CN101121502A discloses a kind of hydrogen production by methanol system and the fuel cell including the system, wraps in system
Methanol cluster hydrogen generating system and CO selective oxidation reaction device are included, the available hydrogen-rich gas CO concentration of system is
50ppm hydrogen below.However the system is by utilizing the exhaust gas of fuel cell to be used for the gasification of methanol-water, and methanol-water
The heat of steam reforming reaction is to carry out combustion reaction to carry out external heating, in this way using external methanol and oxidizing gas
It will cause the increase and consumption of whole system methanol demands amount, and the density of hydrogen for returning to vaporizer is relatively high, in order to control
The temperature of vaporizer certainly will need a large amount of inert gas to reduce the adiabatic temperature of burning, to increase the energy of system
Consumption.
CN104118848A discloses a kind of Methanol cluster hydrogen making reaction device, and main equipment is reactor
Ontology, circular cross-section reactor includes evaporation and reforms, and evaporation plate is evaporated equipped with the stick channel of 0.3-1mm,
Make being evenly distributed for air-flow by the setting in these channels, however the evaporation heat of the above process and the source for reforming heat,
There is no excessive descriptions in patent, and the gas by reforming does not further decrease the list of the CO content in gas
Member is unable to satisfy the needs of fuel cell PEMFC.
CN2668600Y discloses a kind of plate-fin type methanol, mainly includes that two plate-fins change
Hot device and a plate-fin heat reformer, the main function of plate-fin heat exchanger are the gaseous mixtures of Evaporation of methanol water and preheating methanol-water
Body, and heat required for reforming, preheating is mainly from external heat transfer medium, the heat of heat transfer medium is supplied by electric heating
It gives, the plate-fin structure of the system can greatly improve the heat transfer efficiency of system.However above system is just with simple
CO water-gas shift eliminates the CO in mixed gas, CO in the mixed gas generated due to thermodynamic (al) limitation, hydrogen generating system
Content can not be lower than 50ppm, thus be difficult to apply in PEMFC battery system, and heat required for system all by
External supply, further increases the energy consumption of system.
CN102616740A discloses a kind of Methanol cluster hydrogen producer and the method using the equipment hydrogen manufacturing,
Its main method is that methanol-water mixing passes through heat exchanger, vaporizer then into reformer chamber, then passes through preheating temperature controlling machine
Separation chamber of the structure arrival equipped with membrane separator, the available hydrogen in production gas end of membrane separator, the origin of heat of reformer chamber are main
It is the high temperature heat of hydrogen and residual air.The above process passes through through the available pure hydrogen of membrane separator, however above-mentioned system
The evaporation of the methanol-water raw material of system and gasification need outside heat complete, increase the consumption of system capacity；And patent
The heat of middle reformation mainly relies on the thermal capacitance of hydrogen and residual air to complete, and since the specific heat of residual air and hydrogen is smaller, and reforms
The heat needed is bigger, certainly will increase the design difficulty of reformer.
As can be seen from the above patents that the main body of Methanol cluster hydrogen generating system is methanol steam reforming device.Due to
The process is strong endothermic reaction, therefore how to obtain the required energy of Methanol cluster reaction, keeps entire Reforming catalyst
Agent bed temperature is uniformly distributed so that catalyst plays the key points and difficulties that maximum effectiveness is all kinds of reforming reactor designs.
In addition, it is worth noting that, it is all the hydrogen production system employing reforming technology under system of opening wide disclosed in above-mentioned patent, to entire
System exhaust emissions it is of less demanding.For special application, such as space station, airship and certain envelopes for not allowing to discharge
It closed loop border for security reasons will be to inflammable substance such as methanol, H2, CO etc. carry out zero-emission, this is just reformed to entire
More stringent requirements are proposed for the logistics design that can flow of hydrogen fuel cell system, and the imflammable gas in system will be all utilized
Or consumption, but also total system has higher energy efficiency.The present invention proposes a kind of enclosed Methanol cluster
Hydrogen-generating fuel cell hydrogen source system and device.
Summary of the invention
The purpose of the present invention is for above-mentioned hydrogen generating system capacity usage ratio is low or reformate gas in CO content not
Meet the deficiencies such as the requirement of PEMFC fuel cell system, hydrogen generating system integrated level is poor, emission request grade is low, and in view of combustion
Expect the popularity of the application of battery system, the invention proposes a kind of closed hydrogen manufacturing systems for PEMFC fuel cell
System, closed Methanol cluster fuel cell hydrogen source system provided by the invention can not only be made CO concentration and be lower than
The hydrogen-rich reformed gas of 10ppm realizes the closed operation of hydrogen generating system and fuel cell；And pass through effective use fuel cell
Anode exhaust gas improves the energy utilization efficiency of whole system；Pass through burning, reformation, the modular design of CO selective oxidation
And heat-conducting oil system, the bed temperature distribution of reformation, selective oxidation reaction has been advanced optimized, reformation hydrogen production system is realized
That unites is efficient, compact.
The present invention provides a kind of closed-type fuel cell hydrogen source systems, it is characterised in that: the enclosed fuel electricity
Pond hydrogen source system includes methanol feeding mechanism, liquid oxygen apparatus, carbon dioxide storage device, water storage device, conduction oil deposit system
System and hydrogen production units by carbinol system；
Wherein: including combustion evaporator processed, reformer, burner, co selective oxidation in hydrogen production units by carbinol
Reactor and other auxiliary systems；Burner, reformer, evaporator and CO selective oxidation reaction device general module；
The methanol feeding mechanism, liquid oxygen apparatus are connected to the entrance of hydrogen production units by carbinol；Conduction oil stocking system and
The entrance and exit of hydrogen production units by carbinol is connected to；Carbon dioxide storage device, liquid water storage device respectively with hydrogen from methyl alcohol
Entrance and exit connection；
First alcohol and water is entered after reformer by evaporator and obtains reformed gas, is then passed through carbon monoxide and is selected
Selecting property oxidation reactor further decreases the CO concentration of system, is finally passed through fuel cell system and is reacted；Conduction oil passes through
The units such as burner are heated to certain temperature, enter reformer, evaporator carries out returning to conduction oil deposit system after cooling
System；The CO of the unreacted partial tail gas of fuel cell, oxygen and preheating2It is mixed into burner, the water of system generation, titanium dioxide
Carbon respectively enters water storage device and carbon dioxide storage device.
Other described auxiliary systems include that heat conduction oil circulating pump, thermally conductive oil cooler, compressor, clarifier and hydrogen are mixed
Close gas buffer tank；
Conduction oil enters CO selective oxidation reaction device from conduction oil conservation tank by heat conduction oil circulating pump and enters combustion
Thermally conductive oil tank is returned to by reformer, evaporator and cooler after the high temperature heat conductive oil mixing of burner；Clarifier is main
It is to be connected with the outlet of CO selective oxidation reaction device and hydrogen gas mixture surge tank.
The burner is the modular construction of heat transfer form, and the gentle body portion of conduction oil is respectively by the partition of thermal conductivity
Separate, the form of heat conduction baffle can for plate-fin structure, sleeve is finned, metal beehive and tubular heat exchanger formula etc. one
Kind or above-mentioned several assembly；Modular burner uses flanged joint between each other.
The burner side of the modular construction includes combustion catalyst.
The reformer be heat transfer form modular structure, the gentle body portion of conduction oil respectively by the partition of thermal conductivity every
Open, the form of heat conduction baffle can for plate-fin structure, the one kind such as sleeve is finned, metal beehive and tubular heat exchanger formula
Or above-mentioned several assembly；Modular burner uses flanged joint between each other.
Modular reformer side includes methanol-water reforming catalyst.
The operation temperature of modular burner is between 10-600 DEG C, wherein preferably 260-450 DEG C；Operating pressure is
Between 0.1-2MPa；The operation temperature of modular reformer side is 200-350 DEG C, wherein preferably 240-310 DEG C；Operation pressure
Power is between 0.1-4MPa.The type of conduction oil be aromatic hydrocarbons mixture, cycloalkane, tetrahydro how, hydrogenated terphenyl, dibenzyl first
One or several kinds of mixtures of benzene, Long carbon chain saturated hydrocarbons etc..
Be made of inside evaporator conduction oil side and methanol water mix-ture flow side, both sides respectively by the partition of thermal conductivity every
It opens, the form of thermal conductivity partition can be finned plate-fin structure, sleeve, the finned metal beehive of tubulation and tubulation heat exchange
The one kind such as device formula or above-mentioned several assembly；Wherein preferred plate-fin structure, sleeve are finned, tubulation is finned；Evaporator
Modular structure is equally used, uses flanged joint between each other and between reformer.
One heat exchanger is set between reformer and carbon monoxide selective oxidizing reaction device；Heat exchanger and conduction oil recycle
The outlet of pump, the import of burner combustion side, the outlet of reformer reforms side, CO select the import of performance oxidation reactor to be connected
It is logical.
The two sides of carbon monoxide selective oxidizing reaction device are separated by thermal insulation board；The form of thermal conductivity partition can be plate wing
A kind of or above-mentioned several combinations such as formula structure, sleeve are finned, tubulation is finned, metal beehive and tubular heat exchanger formula
Body；Wherein preferred plate-fin structure, sleeve are finned, tubulation is finned；CO selective oxidation reaction device uses modular knot
Structure uses flanged joint between each other and between other heat exchangers.
The reformation gas side of carbon monoxide selective oxidizing reaction device includes selective oxidation catalyst, the main component of catalyst
Iron oxide, nickel oxide, aluminium oxide, oxygen are supported on for the mixture of Pd, Pt, Rh, Au, Ru etc. a kind of or several noble metal
On the carrier of the one or several kinds mixture composition such as SiClx, zirconium oxide, cerium oxide, zinc oxide, magnesia；Either Co, Fe,
Several hopcalites such as Ni, Al, Ce, Zr, Mn, Co；Wherein the bullion content of noble metal catalyst accounts in mass
Between the 0.1%-5% of catalyst quality；Operation temperature is between 80-300 DEG C；It is wherein preferably 100-200 DEG C；Operating pressure
Between 0.1-4MPa.
CO content is lower than 10ppm, and hydrogen gas mixture of the methanol content lower than 100ppm is passed through after fuel cell, utilizes
The unreacted whole tail gas of fuel cell and oxygen mix enter burner；The tail gas of fuel cell is using multistage substep charging
Mode enters burner combustion side.
Water inside clarifier is to come out the system water generated through supercooling using fuel cell and burner, by power
Equipment pump injection clarifier.
Into evaporator methanol from methanol feeding mechanism, water is respectively from methanol purification device, water storage device.
Unreacted methanol in gas is reformed to absorb.Moreover, into the material benzenemethanol water source of evaporator, methanol is come from
In methanol feeding mechanism, water is respectively from methanol purification device, water storage device；It in this way can the whole benefit of methanol in guarantee system
With not being discharged outwardly, improving the utilization rate of methanol and ensure that the safety of system.
Advantages of the present invention:
Closed-type fuel cell hydrogen source system of the present invention, relative to other hydrogen generating systems, overall thinking
Energy, substance distributing rationally and utilize, and has the advantage that
The hydrogen that CO concentration is lower than 10ppm can be not only made in closed-type fuel cell hydrogen production by methanol system provided by the invention
Gas mixes gas, realizes the even running of hydrogen generating system and fuel cell, and by increasing liquid oxygen deposit, water deposit, thermally conductive
The closed operation of total system may be implemented in oil deposit, carbon dioxide deposit.
The characteristics of for PEMFC, avoids reforming externally supplying for heat by the anode exhaust gas of effective use PEMFC,
The consumption for saving methanol fuel, further improves the energy utilization of whole system.
By burning, reformation, the modular design of CO selective oxidation and the use of conduction oil auxiliary system, further
The bed temperature distribution of reformation, selective oxidation reaction is optimized, so that catalyst has higher activity, stability and utilization
Efficiency；By modular design method, variety classes unit is realized, different scales module freely assembles, realize weight
Whole hydrogen generating system it is efficient, compact.
Detailed description of the invention
With reference to the accompanying drawing and embodiment the present invention is described in further detail:
Fig. 1 is closed-type fuel cell hydrogen source system schematic；
In figure, 101 be methanol feeding mechanism, and 102 be conduction oil conservation tank, and 103 be liquid oxygen storage tank, and 201 steam to enter
Device is sent out, 202 be reformer, and 203 be heat exchanger, and 204 be carbon monoxide selective oxidizing reaction device, and 205 be clarifier, and 206 are
Burner, 207 be moisture trap, and 301 be PEMFC battery system.
Specific embodiment
Embodiment 1
Present embodiments provide a kind of closed-type fuel cell hydrogen source system, it is characterised in that: the enclosed fuel
Battery hydrogen source system includes methanol feeding mechanism, liquid oxygen apparatus, carbon dioxide storage device, water storage device, conduction oil deposit
System and hydrogen production units by carbinol system；
Wherein: including combustion evaporator processed, reformer, burner, co selective oxidation in hydrogen production units by carbinol
Reactor and other auxiliary systems；Burner, reformer, evaporator and CO selective oxidation reaction device general module；
The methanol feeding mechanism, liquid oxygen apparatus are connected to the entrance of hydrogen production units by carbinol；Conduction oil stocking system and
The entrance and exit of hydrogen production units by carbinol is connected to；Carbon dioxide storage device, liquid water storage device respectively with hydrogen from methyl alcohol
Entrance and exit connection；
First alcohol and water is entered after reformer by evaporator and obtains reformed gas, is then passed through carbon monoxide and is selected
Property oxidation reactor further decreases the CO concentration of system, is finally passed through fuel cell system and is reacted；Conduction oil passes through combustion
The units such as burner are heated to certain temperature, enter reformer, evaporator carries out returning to conduction oil stocking system after cooling；
The CO of the unreacted partial tail gas of fuel cell, oxygen and preheating2It is mixed into burner, water, the carbon dioxide of system generation
Respectively enter water storage device and carbon dioxide storage device.
Other described auxiliary systems include that heat conduction oil circulating pump, thermally conductive oil cooler, compressor, clarifier and hydrogen are mixed
Close gas buffer tank；
Conduction oil enters CO selective oxidation reaction device from conduction oil conservation tank by heat conduction oil circulating pump and enters combustion
Thermally conductive oil tank is returned to by reformer, evaporator and cooler after the high temperature heat conductive oil mixing of burner；Clarifier is main
It is to be connected with the outlet of CO selective oxidation reaction device and hydrogen gas mixture surge tank.
The burner is the modular construction of heat transfer form, and the gentle body portion of conduction oil is respectively by the partition of thermal conductivity
Separate, the form of heat conduction baffle can for plate-fin structure, sleeve is finned, metal beehive and tubular heat exchanger formula etc. one
Kind or above-mentioned several assembly；Modular burner uses flanged joint between each other.
The burner side of the modular construction includes combustion catalyst.
The reformer be heat transfer form modular structure, the gentle body portion of conduction oil respectively by the partition of thermal conductivity every
Open, the form of heat conduction baffle can for plate-fin structure, sleeve is finned, metal beehive and tubular heat exchanger formula etc. one
Kind or above-mentioned several assembly；Modular burner uses flanged joint between each other.
Modular reformer side includes methanol-water reforming catalyst.
The operation temperature of modular burner is between 10-600 DEG C, wherein preferably 260-450 DEG C；Operating pressure is
Between 0.1-2MPa；The operation temperature of modular reformer side is 200-350 DEG C, wherein preferably 240-310 DEG C；Operation pressure
Power is between 0.1-4MPa.The type of conduction oil be aromatic hydrocarbons mixture, cycloalkane, tetrahydro how, hydrogenated terphenyl, dibenzyl first
One or several kinds of mixtures of benzene, Long carbon chain saturated hydrocarbons etc..
Be made of inside evaporator conduction oil side and methanol water mix-ture flow side, both sides respectively by the partition of thermal conductivity every
It opens, the form of thermal conductivity partition can be finned plate-fin structure, sleeve, the finned metal beehive of tubulation and tubulation heat exchange
The one kind such as device formula or above-mentioned several assembly；Wherein preferred plate-fin structure, sleeve are finned, tubulation is finned；Evaporator
Modular structure is equally used, uses flanged joint between each other and between reformer.
One heat exchanger is set between reformer and carbon monoxide selective oxidizing reaction device；Heat exchanger and conduction oil recycle
The outlet of pump, the import of burner combustion side, the outlet of reformer reforms side, CO select the import of performance oxidation reactor to be connected
It is logical.
The two sides of carbon monoxide selective oxidizing reaction device are separated by thermal insulation board；The form of thermal conductivity partition can be plate wing
A kind of or above-mentioned several combinations such as formula structure, sleeve are finned, tubulation is finned, metal beehive and tubular heat exchanger formula
Body；Wherein preferred plate-fin structure, sleeve are finned, tubulation is finned；CO selective oxidation reaction device uses modular knot
Structure uses flanged joint between each other and between other heat exchangers.
The reformation gas side of carbon monoxide selective oxidizing reaction device include selective oxidation catalyst, catalyst it is main at
Be divided into a kind of or several noble metal such as Pd, Pt, Rh, Au, Ru mixture be supported on iron oxide, nickel oxide, aluminium oxide,
On the carrier of the one or several kinds mixture composition such as silica, zirconium oxide, cerium oxide, zinc oxide, magnesia；Either Co,
Several hopcalites such as Fe, Ni, Al, Ce, Zr, Mn, Co；Wherein the bullion content of noble metal catalyst is in mass
It accounts between the 0.1%-5% of catalyst quality；Operation temperature is between 80-300 DEG C；It is wherein preferably 100-200 DEG C；Operation pressure
Power is between 0.1-4MPa.
CO content is lower than 10ppm, and hydrogen gas mixture of the methanol content lower than 100ppm is passed through after fuel cell, utilizes
The unreacted whole tail gas of fuel cell and oxygen mix enter burner；The tail gas of fuel cell is using multistage substep charging
Mode enters burner combustion side.
Water inside clarifier is to come out the system water generated through supercooling using fuel cell and burner, by power
Equipment pump injection clarifier.
Into evaporator methanol from methanol feeding mechanism, water is respectively from methanol purification device, water storage device.
Unreacted methanol in gas is reformed to absorb.Moreover, into the material benzenemethanol water source of evaporator, methanol is come from
In methanol feeding mechanism, water is respectively from methanol purification device, water storage device；It in this way can the whole benefit of methanol in guarantee system
With not being discharged outwardly, improving the utilization rate of methanol and ensure that the safety of system.
As shown in Figure 1.Water in methanol feeding mechanism 101 and clarifier 205 respectively after pump increases to 0.5MPa pressure,
Heat of vaporization is absorbed after into evaporator 201 into gaseous state, heat required for evaporating is supplied by high temperature heat conductive oil.Methanol-water steams
Vapour enters progress Methanol cluster reaction in the reformer 202 equipped with reforming catalyst, Methanol cluster reaction
The heat of absorption is also to be supplied by high temperature heat conductive oil, can be by weight by regulating and controlling the temperature and flow of high temperature heat conductive oil
Uniformly, after reformer, steam reforming reaction, the reformation gas of generation occur for methanol and water vapour for the temperature control of whole device
Containing hydrogen, carbon dioxide, water vapour, part carbon monoxide and minimal amount of methanol.Then high temperature reformation gas is by changing
Hot device 203 cool between 100-150 DEG C, and the cold fluid of heat exchanger 203 is mainly by conduction oil.Then it reforms gas and comes
Enter carbon monoxide selective oxidizing reaction device 204 from the oxygen of liquid oxygen storage tank 103 to be catalyzed in co selective oxidation
Oxidation of Carbon Monoxide reaction is carried out in agent, co selective oxidation is an exothermic reaction, and the heat released is mainly
It is taken away by way of conduction oil Absorption of Medium heat.By an oxidation in the reformation gas of carbon monoxide selective oxidizing reaction device
Carbon content significantly reduces, and the carbon monoxide content of butt is lower than 10ppm, by carbon monoxide selective oxidizing reaction device
Hydrogen mixed gas temperature is reduced between 60-80 DEG C.Then by containing the cooling water in moisture trap 207 in water purification
In device 205, the Trace Methanol in gas will be reformed and purified.Reform in this way main group of gas become hydrogen, carbon dioxide, water vapour and
Butt is less than the carbon monoxide of 10ppm, and hydrogen gas mixture enters the anode of PEMFC and from liquid oxygen storage device 103
Oxygen be electrochemically reacted, and chemical energy is transformed into electric energy.Unreacted hydrogen mixed gas in a fuel cell
Body and oxygen mix from liquid oxygen storage device 103 enter in burner 206 and hydrogen occur on the surface of combustion catalyst
Oxygen combustion reaction, the heat of releasing mainly pass through cooling medium conduction oil and take away.The burning gases that burner comes out include two
The water of carbonoxide and partial condensation carries out gas-water separation then into carbonated drink cooler 207, and isolated carbon dioxide is through over-voltage
Contracting machine is compressed to 0.5-0.6MPa and enters in carbon dioxide storage device, the liquid water one separated in moisture trap
Part enters water storage device, a part be injected into clarifier 205 by power-equipment pump carry out it is micro- in absorption reformer
Measure methanol.
The circulation of conduction oil in the present system is as follows: the conduction oil from conduction oil conservation tank 102 is pressurized to one by pumping
Under fixed pressure, a part of conduction oil is entered in burner 206 and is exchanged heat, and other conduction oils have respectively entered an oxygen
Change carbon selectivity oxidation reactor 204, the high temperature heat conductive oil to exchange heat in heat exchanger 203 and the height from burner 206
After warm conduction oil mixing enters reformer 202 later, evaporator 201 is exchanged heat, the conduction oil after cooling reaches conjunction
Suitable temperature returns in conduction oil storage device 102, recycles.
Claims (9)
1. a kind of closed-type fuel cell hydrogen source system, it is characterised in that: the closed-type fuel cell hydrogen source system includes
Methanol feeding mechanism, liquid oxygen apparatus, carbon dioxide storage device, water storage device, conduction oil stocking system and hydrogen from methyl alcohol dress
Set system；
Wherein: including combustion evaporator processed, reformer, burner, carbon monoxide selective oxidizing reaction in hydrogen production units by carbinol
Device and other auxiliary systems；Burner, reformer, evaporator and carbon monoxide selective oxidizing reaction device general module
Change；
The methanol feeding mechanism, liquid oxygen apparatus are connected to the entrance of hydrogen production units by carbinol system；Conduction oil stocking system and
The entrance and exit of hydrogen production units by carbinol system is connected to；The water storage device entrance and exit with hydrogen production units by carbinol system respectively
Connection.
2. closed-type fuel cell hydrogen source system described in accordance with the claim 1, it is characterised in that: other described auxiliary systems
Including heat conduction oil circulating pump, thermally conductive oil cooler, compressor, clarifier and hydrogen gas mixture surge tank；Conduction oil is by thermally conductive
Oil circulating pump enters carbon monoxide selective oxidizing reaction device from conduction oil conservation tank and enters the high-temperature heat-conductive of burner
Thermally conductive oil tank is returned to by reformer, evaporator and cooler after oil mixing；Clarifier is mainly selected with carbon monoxide
The outlet of selecting property oxidation reactor and hydrogen gas mixture surge tank are connected.
3. closed-type fuel cell hydrogen source system described in accordance with the claim 1, it is characterised in that: the burner is heat exchange
The modular construction of form, the gentle body portion of conduction oil are separated by the partition of thermal conductivity respectively, and the form of heat conduction baffle is plate
Wing formula structure, sleeve be finned, one of metal beehive and tubular heat exchanger formula or above-mentioned several assembly；Modularization
Burner use flanged joint between each other.
4. closed-type fuel cell hydrogen source system described in accordance with the claim 3, it is characterised in that: the modular construction
Burner side includes combustion catalyst.
5. closed-type fuel cell hydrogen source system described in accordance with the claim 1, it is characterised in that: the reformer is heat exchange
The modular structure of form, the gentle body portion of conduction oil are separated by the partition of thermal conductivity respectively, and the form of heat conduction baffle is plate wing
Formula structure, sleeve be finned, one of metal beehive and tubular heat exchanger formula or above-mentioned several assembly；It is modular
Burner uses flanged joint between each other.
6. closed-type fuel cell hydrogen source system according to claim 5, it is characterised in that: modular reformer side packet
Reforming catalyst containing methanol-water.
7. closed-type fuel cell hydrogen source system described in accordance with the claim 1, it is characterised in that: by conduction oil inside evaporator
Side and methanol water mix-ture flow side composition, both sides are separated by the partition of thermal conductivity respectively, and the form of thermal insulation board is plate-fin knot
Structure, sleeve are finned, one of the finned metal beehive of tubulation and tubular heat exchanger formula or above-mentioned several assembly；It steams
Hair device equally uses modular structure, uses flanged joint between each other and between reformer.
8. closed-type fuel cell hydrogen source system described in accordance with the claim 1, it is characterised in that: reformer and carbon monoxide choosing
One heat exchanger is set between selecting property oxidation reactor；The outlet of heat exchanger and heat conduction oil circulating pump, burner combustion side into
The outlet of mouth, reformer reforms side, the import of carbon monoxide selective energy oxidation reactor are connected.
9. closed-type fuel cell hydrogen source system described in accordance with the claim 1, it is characterised in that: co selective oxidation
The two sides of reactor are separated by thermal insulation board；The form of thermal insulation board is plate-fin structure, sleeve is finned, tubulation is finned, metal
One of honeycomb and tubular heat exchanger formula or above-mentioned several assembly；Carbon monoxide selective oxidizing reaction device uses mould
The structure of block uses flanged joint between each other and between other heat exchangers.
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| CN106898794B (en) * | 2017-04-20 | 2019-08-23 | 武汉理工大学 | A kind of electricity-generating method and power generator based on methanol steam reforming system |
| CN109273745B (en) * | 2018-10-29 | 2024-04-12 | 浙江氢谷新能源汽车有限公司 | Integrated fuel cell device for pure electric automobile |
| CN109546189B (en) * | 2018-10-29 | 2021-10-22 | 南京航空航天大学 | Multi-stage reforming power generation system using liquid fuel oil as hydrogen source of fuel cell |
| CN110040685B (en) * | 2019-04-29 | 2020-09-25 | 北京铂陆氢能科技开发有限公司 | Liquid organic hydrogen storage material |
| CN110649287B (en) * | 2019-09-30 | 2021-03-16 | 潍柴动力股份有限公司 | Fuel cell engine system, gas supply system thereof and control method |
| CN112194100A (en) * | 2020-11-16 | 2021-01-08 | 王海东 | Conduction oil-free methanol water hydrogen production device for recycling carbon dioxide |
| CN116979107B (en) * | 2023-09-25 | 2023-12-19 | 成都岷山绿氢能源有限公司 | Fuel cell system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101980954A (en) * | 2009-01-27 | 2011-02-23 | 松下电器产业株式会社 | Fuel processing device, fuel cell system provided therewith, and method for operating a fuel processing device |
| CN102287917A (en) * | 2011-06-01 | 2011-12-21 | 刘革 | Heating system of methanol hydrogen-production oxidation |
| CN202189866U (en) * | 2011-08-18 | 2012-04-11 | 上海中垚科技发展有限公司 | Totally-enclosed type power supply system for mine escape capsule |
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| KR101282578B1 (en) * | 2006-04-14 | 2013-07-04 | 삼성에스디아이 주식회사 | reformer with double heater and fuel cell system using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101980954A (en) * | 2009-01-27 | 2011-02-23 | 松下电器产业株式会社 | Fuel processing device, fuel cell system provided therewith, and method for operating a fuel processing device |
| CN102287917A (en) * | 2011-06-01 | 2011-12-21 | 刘革 | Heating system of methanol hydrogen-production oxidation |
| CN202189866U (en) * | 2011-08-18 | 2012-04-11 | 上海中垚科技发展有限公司 | Totally-enclosed type power supply system for mine escape capsule |
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