CN105720285A - Enclosed fuel cell hydrogen source system - Google Patents
Enclosed fuel cell hydrogen source system Download PDFInfo
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- CN105720285A CN105720285A CN201410741183.2A CN201410741183A CN105720285A CN 105720285 A CN105720285 A CN 105720285A CN 201410741183 A CN201410741183 A CN 201410741183A CN 105720285 A CN105720285 A CN 105720285A
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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
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Abstract
The invention provides an enclosed fuel cell hydrogen source system, which comprises a methanol supply device, a liquid oxygen device, a carbon dioxide storage device, a water storage device, a heat-conducting oil storage system and a methanol hydrogen production device system, wherein the methanol hydrogen production device comprises a hydrogen production combustion evaporator, a reformer, a combustor, a carbon monoxide selectivity oxidation reactor and other auxiliary systems; the combustor, the reformer, the evaporator and the CO selectivity oxidation reactor are integrally modularized; the methanol supply device and the liquid oxygen device communicates with an inlet of the methanol hydrogen production device; the heat-conducting oil storage system communicates with the inlet and an outlet of the methanol hydrogen production device; and the carbon dioxide storage device and the liquid water storage device communicate with the inlet and the outlet of the methanol hydrogen production device respectively. The enclosed fuel cell hydrogen source system has the advantages that enclosed operation of the whole system is achieved; consumption of methanol fuel is reduced; energy utilization of the whole system is further improved; and the structure of a reforming hydrogen production system is compact.
Description
Technical field
The present invention relates to closed hydrocarbon fuels reformation hydrogen production field, particularly to a kind of closed-type fuel cell hydrogen source system.
Background technology
Hydrogen reserves on earth are very abundant, and combustion heat value is high, and do not produce any pollution after burning, therefore are counted as 21 century desirably clean new forms of energy.It is that Hydrogen Technology applies most important aspect that Hydrogen Energy is converted into electric energy, and with fuel cell abreast of the times development especially that hydrogen is fuel.Fuel cell is a kind of to utilize redox reaction that the chemical energy in material is converted into the device of electric energy, and its 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 is low, adapt to the advantage that different capacity requires so that it is have good prospect in market application aspect.
In numerous kinds of fuel cells, Proton Exchange Membrane Fuel Cells (PEMFC) due to near-zero release, start convenient, specific power big, operation temperature low (50-80 DEG C), easily get rid of without electrolyte loss, water, the feature such as long service life, it is shown that powerful application prospect.PEMFC can not only be applied in space and military affairs, it is also possible to is applied on the vehicles such as automobile as novel portable power power supply.But, the fuel of PEMFC is hydrogen, due to gaseous state hydrogen-feeding system is too huge and also liquified hydrogen again can the substantial amounts of energy of loss, be unsuitable in onboard system.And, hydrogen is a kind of inflammable and explosive gas, is not easy to discover during leakage, and therefore, PEMFC uses on a large scale, it is necessary to solve the storage of hydrogen, transport and safety problem.
The solution overcoming the problems referred to above is the scene used at fuel cell, utilizes fuel hydrogen generating system, quickly prepares the qualified hydrogen-rich mixed gas that fuel cell needs from the Hydrocarbon such as methanol, natural gas, liquefied gas, gasoline, diesel oil.The combined system of above-mentioned fuel hydrogen manufacturing and fuel cell is considered as the mode that commercializing fuel cells application is maximally efficient.This class A fuel A hydrogen generating system generally through multiple conversion processes, just can obtain the hydrogen-rich mixed gas that fuel cell needs.Compared with other Hydrocarbon, hydrogen from methyl alcohol has obvious advantage: for liquid under methanol room temperature, transports convenience, wide material sources, except the Fossil fuels such as commodity petroleum, natural gas and coal, it is also possible to prepared by renewable biomass even municipal refuse；Additionally, hydrogen from methyl alcohol reaction condition is gentle, reforming conversion is high, not easily carbon distribution, there is significantly high H/C ratio, in product, hydrogen content is high, and CO content is low.Therefore, methanol is considered as the desirable feedstock of fuel cell hydrogen-feeding.
In preparing hydrogen by reforming methanol reaction, mainly there is Methanol cluster hydrogen manufacturing (MSR), methanol fractions oxidation catalysis reformation hydrogen production (POR) and three kinds of methods of methanol nature catalytically reforming hydrogen producing (ATR), wherein the chemical equation of Methanol cluster is as follows:
CH3OH+H2O→CO2+3H2ΔH298=49.5kJ/mol
From atom economy angle, methanol steam catalytically reforming hydrogen producing is the reaction that in methanol recapitalization system, hydrogen manufacturing content is the highest, and equimolar first alcohol and water, under the effect of catalyst, generates the carbon dioxide of a mole and the hydrogen of three moles.Methanol cluster hydrogen manufacturing system have a major advantage in that reaction condition is gentle, in product, hydrogen content is high, and by-product CO concentration is relatively low.This is for providing reliable hydrogen source of crucial importance for PEMFC.Because the CO in hydrogen-rich reformed gas is the poisonous substance of PEMFC electrode Pt catalyst, a small amount of CO can cause catalyst poisoning thus reducing the activity of eelctro-catalyst, causes the decline of battery performance.Therefore generally, it is provided that to the hydrogen-rich reformed gas fuel requirement of PEMFC, CO content therein is down to below 10ppm.
CN101121502A discloses a kind of hydrogen production by methanol system and includes the fuel cell of this system, and its system includes Methanol cluster hydrogen generating system and CO selective oxidation reaction device, and it is the hydrogen of below 50ppm that system can obtain hydrogen-rich gas CO concentration.But this system is by utilizing the waste gas gasification for methanol-water of fuel cell, and the heat of Methanol cluster reaction is to adopt external methanol and oxidizing gas to carry out combustion reaction to carry out outside heat supply, so can cause increase and the consumption of whole system methanol demands amount, and the density of hydrogen that returns vaporizer is higher, in order to control the temperature of vaporizer, substantial amounts of noble gas certainly will be needed to reduce the adiabatic temperature of burning, thus adding the energy expenditure of system.
CN104118848A discloses a kind of Methanol cluster hydrogen making reaction device, its main equipment is reactor body, circular cross-section reactor includes evaporation and reforms, and evaporation plate is provided with the stick channel of 0.3-1mm and is evaporated, being evenly distributed of air-flow is made by the setting of these passages, but the source of the evaporation heat of said process and reformation heat, description not too much in patent, and the gas through reforming does not reduce the unit of the CO content in gas further, it is impossible to meet the needs of fuel cell PEMFC.
CN2668600Y discloses a kind of plate-fin type methanol, it mainly includes two plate-fin heat exchangers and a plate-fin heat reformer, the Main Function of plate-fin heat exchanger is Evaporation of methanol water and the mixing gas of preheating methanol-water, and reform, preheat required heat and mainly come from the heat transfer medium of outside, the heat of heat transfer medium is supplied by electrical heating, and the plate-fin structure of this system can be greatly improved the heat transfer efficiency of system.But said system is to eliminate the CO in mixing gas just with simple CO water-gas shift, due to thermodynamic (al) restriction, in the mixing gas that its hydrogen generating system produces, CO content can not lower than 50ppm, thus it is difficult to apply in PEMFC battery system, and the heat required for system is all by outside supply, further increases the energy expenditure of system.
CN102616740A discloses a kind of Methanol cluster hydrogen producer and the method utilizing this equipment hydrogen manufacturing, its main method is that methanol-water mixes by heat exchanger, vaporizer then into reformer chamber, then pass through preheating temperature control mechanism and arrive the separation chamber equipped with membrane separator, the aerogenesis end of membrane separator can obtain hydrogen, and the origin of heat of reformer chamber is mainly the heat of high temperature of hydrogen and residual air.Said process is through obtaining pure hydrogen by membrane separator, but the evaporation of the methanol-water raw material of said system and the heat outside needing that gasifies complete, and add the consumption of system capacity；And the heat reformed in patent mainly relies on the thermal capacitance of hydrogen and residual air to complete, owing to the specific heat of residual air and hydrogen is smaller, and the heat needed of reforming is relatively larger, certainly will add the design difficulty of reformer.
By above-mentioned patent it can be seen that the main body of Methanol cluster hydrogen generating system is methanol steam reforming device.Owing to this process is strong endothermic reaction, therefore how to obtain the energy that Methanol cluster reaction is required, keep being uniformly distributed so that catalyst plays the emphasis and difficult point that maximum effectiveness is the design of all kinds of reforming reactor of whole reforming catalyst bed temperature.
Additionally, it is worthy of note, disclosed in above-mentioned patent is all open wide the hydrogen production system employing reforming technology under system, less demanding to whole system exhaust emissions.For special application scenario, as space station, airship and some do not allow the enclosed environment of discharge, for security reasons, will to inflammable substance such as methanol, H2, CO etc. carry out zero-emission, the logistics that can flow of whole reformer hydrogen fuel cell system is just designed and has higher requirement by this, and the imflammable gas in system will all be utilized or consumes, and also makes total system have higher energy efficiency.Namely the present invention proposes a kind of enclosed Methanol cluster hydrogen-generating fuel cell hydrogen source system and device.
Summary of the invention
It is an object of the invention to that the capacity usage ratio for above-mentioned hydrogen generating system is low or in reformate gas, the content of CO is unsatisfactory for the deficiencies such as PEMFC fuel cell system requires, hydrogen generating system integrated level is poor, emission request grade is low, and consider the popularity of the application scenario of fuel cell system, the present invention proposes a kind of closed hydrogen generating system for PEMFC fuel cell, closed Methanol cluster fuel cell hydrogen origin system provided by the invention is possible not only to prepare the CO concentration hydrogen-rich reformed gas lower than 10ppm, it is achieved the closed operation of hydrogen generating system and fuel cell；And by effectively utilizing the anode exhaust gas of fuel cell, improve the energy utilization efficiency of whole system；By burning, reforming, the modular design of CO selective oxidation and heat-conducting oil system, optimize reformations further, the bed temperature of selective oxidation reaction is distributed, it is achieved that hydrogen production system employing reforming technology efficient, compact.
The invention provides a kind of closed-type fuel cell hydrogen source system, it is characterised in that: described 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 production units by carbinol system；
Wherein: hydrogen production units by carbinol includes combustion evaporator processed, reformer, burner, carbon monoxide selective oxidizing reaction device and other aid systems；The general module of burner, reformer, vaporizer and CO selective oxidation reaction device；
Described methanol feeding mechanism, liquid oxygen apparatus connect with the entrance of hydrogen production units by carbinol；Conduction oil stocking system connects with the entrance and exit of hydrogen production units by carbinol；Carbon dioxide storage device, aqueous water storage device connect with the entrance and exit of hydrogen from methyl alcohol respectively；
First alcohol and water enter into reformer by vaporizer after obtain reformed gas, then pass through carbon monoxide selective oxidizing reaction device and reduce the CO concentration of system further, finally pass into fuel cell system and react；Conduction oil is heated to certain temperature by unit such as burners, enters into reformer, vaporizer returns to conduction oil stocking system after cooling down；The CO of the unreacted partial tail gas of fuel cell, oxygen and preheating2Being mixed into burner, water, carbon dioxide that system generates respectively enter water storage device and carbon dioxide storage device.
Other described aid systems include heat conduction oil circulating pump, conduction oil cooler, compressor, depurator and hydrogen gas mixture surge tank；
Conduction oil is entered into after CO selective oxidation reaction device mixes with the high temperature heat conductive oil entering into burner from conduction oil conservation tank by heat conduction oil circulating pump and returns to conduction oil storage tank through reformer, vaporizer and cooler；Depurator is mainly connected with outlet and the hydrogen gas mixture surge tank of CO selective oxidation reaction device.
Described burner is the modular construction of heat exchange form, the gentle body portion of conduction oil is separated by the dividing plate of heat conductivity respectively, and the form of its heat conduction baffle can be that plate-fin structure, sleeve be finned, metal beehive and tubular heat exchanger formula etc. are a kind of or above-mentioned several assembly；Modular burner adopts Flange joint each other.
The burner side of described modular construction comprises combustion catalyst.
Described reformer is the modular structure of heat exchange form, the gentle body portion of conduction oil is separated by the dividing plate of heat conductivity respectively, and the form of its heat conduction baffle can be that plate-fin structure, sleeve be finned, metal beehive and tubular heat exchanger formula etc. are a kind of or above-mentioned several assembly；Modular burner adopts Flange joint each other.
Modular reformer side comprises methanol-water reforming catalyst.
Between the operation temperature of modular burner is 10-600 DEG C, wherein it is preferably 260-450 DEG C；Operation pressure is between 0.1-2MPa；The operation temperature of modular reformer side is 200-350 DEG C, is wherein preferably 240-310 DEG C；Operation pressure is between 0.1-4MPa.The kind of conduction oil be aromatic hydrocarbons mixture, cycloalkane, tetrahydrochysene how, one or several mixture of hydrogenated terphenyl, dibenzyl toluene, Long carbon chain saturated hydrocarbons etc..
It is made up of conduction oil side and methanol water mix-ture flow side inside vaporizer, both sides are separated by the dividing plate of heat conductivity respectively, and the form of heat conductivity dividing plate can be that plate-fin structure, sleeve be finned, the finned metal beehive of tubulation and tubular heat exchanger formula etc. are a kind of or above-mentioned several assembly；Wherein preferably plate-fin structure, sleeve is finned, tubulation is finned；Vaporizer adopts modular structure equally, each other and and reformer between adopt Flange joint.
One heat exchanger is set between reformer and carbon monoxide selective oxidizing reaction device；The outlet of heat exchanger and heat conduction oil circulating pump, the import of burner combustion side, reformer reforms side outlet, CO selects the import of performance oxidation reactor to be connected.
The both sides of carbon monoxide selective oxidizing reaction device are separated by thermal insulation board；The form of heat conductivity dividing plate can be plate-fin structure, sleeve is finned, tubulation is finned, metal beehive and tubular heat exchanger formula etc. are a kind of or above-mentioned several assembly；Wherein preferably plate-fin structure, sleeve is finned, tubulation is finned；CO selective oxidation reaction device adopt modular structure, each other and and other heat exchangers between adopt Flange joint.
The reformation gas side of carbon monoxide selective oxidizing reaction device comprises selective oxidation catalyst, and the mixture load being mainly composed of a kind of or several noble metal such as Pd, Pt, Rh, Au, Ru of catalyst is on the carrier of one or several mixture compositions such as ferrum oxide, nickel oxide, aluminium oxide, silicon oxide, zirconium oxide, cerium oxide, zinc oxide, magnesium oxide；Or several hopcalite such as Co, Fe, Ni, Al, Ce, Zr, Mn, Co；Wherein the bullion content of noble metal catalyst accounts between the 0.1%-5% of catalyst quality in mass；Between operation temperature is 80-300 DEG C；Wherein it is preferably 100-200 DEG C；Operation pressure is between 0.1-4MPa.
CO content is lower than 10ppm, after the methanol content hydrogen gas mixture lower than 100ppm passes into fuel cell, utilizes the unreacted whole tail gas of fuel cell and oxygen mix to enter burner；The tail gas of fuel cell adopts the mode of multistage substep charging to enter burner combustion side.
Water within depurator is the system water adopting fuel cell and burner out to generate through supercooling, enters depurator through power-equipment infusion.
The methanol entering vaporizer comes from methanol feeding mechanism, and water is respectively from methanol purification device, water storage device.
In order to absorb unreacted methanol in reformation gas.And, entering the material benzenemethanol water source of vaporizer, methanol comes from methanol feeding mechanism, and water is respectively from methanol purification device, water storage device；So can ensure that methanol in system all of, it does not have outwardly discharge, improve 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 system, overall thinking energy, the distributing rationally and utilizing of material, have the advantage that
Closed-type fuel cell hydrogen production by methanol system provided by the invention is possible not only to prepare the mixed gas of the CO concentration hydrogen lower than 10ppm, realize the even running of hydrogen generating system and fuel cell, and by increasing liquid oxygen deposit, water deposit, conduction oil deposit, carbon dioxide deposit can realize the closed operation of total system.
For the feature of PEMFC, by effectively utilizing the anode exhaust gas of PEMFC, it is to avoid being externally supplied of reformation heat, save the consumption of methanol fuel, further increase the Energy harvesting of whole system.
By burning, reforming, the use of the modular design of CO selective oxidation and conduction oil aid system, optimize reformations further, the bed temperature of selective oxidation reaction is distributed so that catalyst has higher activity, stability and utilization ratio；By modular design, it is achieved that variety classes unit, freely the assembling of different scales module, it is achieved that hydrogen production system employing reforming technology efficient, compact.
Accompanying drawing explanation
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation:
Fig. 1 is closed-type fuel cell hydrogen source system schematic；
In figure, 101 is methanol feeding mechanism, and 102 is conduction oil conservation tank, and 103 is liquid oxygen storage tank, 201 for entering vaporizer, 202 is reformer, and 203 is heat exchanger, and 204 is carbon monoxide selective oxidizing reaction device, 205 is depurator, 206 is burner, and 207 is moisture trap, and 301 is PEMFC battery system.
Detailed description of the invention
Embodiment 1
Present embodiments provide a kind of closed-type fuel cell hydrogen source system, it is characterised in that: described 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 production units by carbinol system；
Wherein: hydrogen production units by carbinol includes combustion evaporator processed, reformer, burner, carbon monoxide selective oxidizing reaction device and other aid systems；The general module of burner, reformer, vaporizer and CO selective oxidation reaction device；
Described methanol feeding mechanism, liquid oxygen apparatus connect with the entrance of hydrogen production units by carbinol；Conduction oil stocking system connects with the entrance and exit of hydrogen production units by carbinol；Carbon dioxide storage device, aqueous water storage device connect with the entrance and exit of hydrogen from methyl alcohol respectively；
First alcohol and water enter into reformer by vaporizer after obtain reformed gas, then pass through carbon monoxide selective oxidizing reaction device and reduce the CO concentration of system further, finally pass into fuel cell system and react；Conduction oil is heated to certain temperature by unit such as burners, enters into reformer, vaporizer returns to conduction oil stocking system after cooling down；The CO of the unreacted partial tail gas of fuel cell, oxygen and preheating2Being mixed into burner, water, carbon dioxide that system generates respectively enter water storage device and carbon dioxide storage device.
Other described aid systems include heat conduction oil circulating pump, conduction oil cooler, compressor, depurator and hydrogen gas mixture surge tank；
Conduction oil is entered into after CO selective oxidation reaction device mixes with the high temperature heat conductive oil entering into burner from conduction oil conservation tank by heat conduction oil circulating pump and returns to conduction oil storage tank through reformer, vaporizer and cooler；Depurator is mainly connected with outlet and the hydrogen gas mixture surge tank of CO selective oxidation reaction device.
Described burner is the modular construction of heat exchange form, the gentle body portion of conduction oil is separated by the dividing plate of heat conductivity respectively, and the form of its heat conduction baffle can be that plate-fin structure, sleeve be finned, metal beehive and tubular heat exchanger formula etc. are a kind of or above-mentioned several assembly；Modular burner adopts Flange joint each other.
The burner side of described modular construction comprises combustion catalyst.
Described reformer is the modular structure of heat exchange form, the gentle body portion of conduction oil is separated by the dividing plate of heat conductivity respectively, and the form of its heat conduction baffle can be that plate-fin structure, sleeve be finned, metal beehive and tubular heat exchanger formula etc. are a kind of or above-mentioned several assembly；Modular burner adopts Flange joint each other.
Modular reformer side comprises methanol-water reforming catalyst.
Between the operation temperature of modular burner is 10-600 DEG C, wherein it is preferably 260-450 DEG C；Operation pressure is between 0.1-2MPa；The operation temperature of modular reformer side is 200-350 DEG C, is wherein preferably 240-310 DEG C；Operation pressure is between 0.1-4MPa.The kind of conduction oil be aromatic hydrocarbons mixture, cycloalkane, tetrahydrochysene how, one or several mixture of hydrogenated terphenyl, dibenzyl toluene, Long carbon chain saturated hydrocarbons etc..
It is made up of conduction oil side and methanol water mix-ture flow side inside vaporizer, both sides are separated by the dividing plate of heat conductivity respectively, and the form of heat conductivity dividing plate can be that plate-fin structure, sleeve be finned, the finned metal beehive of tubulation and tubular heat exchanger formula etc. are a kind of or above-mentioned several assembly；Wherein preferably plate-fin structure, sleeve is finned, tubulation is finned；Vaporizer adopts modular structure equally, each other and and reformer between adopt Flange joint.
One heat exchanger is set between reformer and carbon monoxide selective oxidizing reaction device；The outlet of heat exchanger and heat conduction oil circulating pump, the import of burner combustion side, reformer reforms side outlet, CO selects the import of performance oxidation reactor to be connected.
The both sides of carbon monoxide selective oxidizing reaction device are separated by thermal insulation board；The form of heat conductivity dividing plate can be plate-fin structure, sleeve is finned, tubulation is finned, metal beehive and tubular heat exchanger formula etc. are a kind of or above-mentioned several assembly；Wherein preferably plate-fin structure, sleeve is finned, tubulation is finned；CO selective oxidation reaction device adopt modular structure, each other and and other heat exchangers between adopt Flange joint.
The reformation gas side of carbon monoxide selective oxidizing reaction device comprises selective oxidation catalyst, and the mixture load being mainly composed of a kind of or several noble metal such as Pd, Pt, Rh, Au, Ru of catalyst is on the carrier of one or several mixture compositions such as ferrum oxide, nickel oxide, aluminium oxide, silicon oxide, zirconium oxide, cerium oxide, zinc oxide, magnesium oxide；Or several hopcalite such as Co, Fe, Ni, Al, Ce, Zr, Mn, Co；Wherein the bullion content of noble metal catalyst accounts between the 0.1%-5% of catalyst quality in mass；Between operation temperature is 80-300 DEG C；Wherein it is preferably 100-200 DEG C；Operation pressure is between 0.1-4MPa.
CO content is lower than 10ppm, after the methanol content hydrogen gas mixture lower than 100ppm passes into fuel cell, utilizes the unreacted whole tail gas of fuel cell and oxygen mix to enter burner；The tail gas of fuel cell adopts the mode of multistage substep charging to enter burner combustion side.
Water within depurator is the system water adopting fuel cell and burner out to generate through supercooling, enters depurator through power-equipment infusion.
The methanol entering vaporizer comes from methanol feeding mechanism, and water is respectively from methanol purification device, water storage device.
In order to absorb unreacted methanol in reformation gas.And, entering the material benzenemethanol water source of vaporizer, methanol comes from methanol feeding mechanism, and water is respectively from methanol purification device, water storage device；So can ensure that methanol in system all of, it does not have outwardly discharge, improve the utilization rate of methanol and ensure that the safety of system.
As shown in Figure 1.Water in methanol feeding mechanism 101 and depurator 205 increases after 0.5MPa pressure respectively through pump, absorbs heat of vaporization and become gaseous state after entering vaporizer 201, and the heat required for evaporation is supplied by high temperature heat conductive oil.Methanol steam enters into equipped with carrying out Methanol cluster reaction in the reformer 202 of reforming catalyst, the heat of Methanol cluster reactive absorption is also supplied by high temperature heat conductive oil, by regulating and controlling temperature and the flow of high temperature heat conductive oil, can the temperature of reformer be controlled uniformly, after reformer, methanol and water vapour generation steam reforming reaction, the reformation gas of generation contain hydrogen, carbon dioxide, water vapour, part carbon monoxide and minimal amount of methanol.Then high temperature reformation gas is undertaken cooling between 100-150 DEG C by heat exchanger 203, and the cold flow body of heat exchanger 203 is mainly by conduction oil.Then reformation gas and the oxygen entrance carbon monoxide selective oxidizing reaction device 204 from liquid oxygen storage tank 103 carry out Oxidation of Carbon Monoxide reaction on carbon monoxide selective oxidizing catalyst, co selective oxidation is an exothermic reaction, and its liberated heat is taken away mainly by the mode of conduction oil Absorption of Medium heat.In the reformation gas of carbon monoxide selective oxidizing reaction device, carbon monoxide content significantly reduces, and the carbon monoxide content of its butt is lower than 10ppm, and the hydrogen mixed gas temperature through carbon monoxide selective oxidizing reaction device is reduced between 60-80 DEG C.Be then passed through containing from the cooling water in moisture trap 207 in water purifier 205, by reformation gas Trace Methanol purify.Such reformation gas mainly comprise as carbon monoxide less than 10ppm of hydrogen, carbon dioxide, water vapour and butt, hydrogen gas mixture enters into the anode of PEMFC and is electrochemically reacted with the oxygen coming from liquid oxygen storage device 103, and chemical energy is become electric energy.Unreacted hydrogen gas mixture and the oxygen mix from liquid oxygen storage device 103 enter in burner 206 and oxyhydrogen combustion reaction occur on the surface of combustion catalyst in a fuel cell, and liberated heat is taken away mainly by cooling medium conduction oil.Burner burning gases out include the water of carbon dioxide and partial condensation, gas-water separation is carried out then into soda pop cooler 207, the carbon dioxide separated enters in carbon dioxide storage device through compressor compresses to 0.5-0.6MPa, the aqueous water separated in moisture trap is partly into water storage device, and a part is injected in depurator 205 by power-equipment pump and carries out the Trace Methanol in absorption reformer.
Conduction oil circulation in the present system is as follows: the conduction oil coming from conduction oil conservation tank 102 is pressurized under certain pressure by pump, the conduction oil of a part enters into and carries out heat exchange in burner 206, other conduction oil has respectively entered carbon monoxide selective oxidizing reaction device 204, the high temperature heat conductive oil that in heat exchanger 203, heat exchange obtains and come from burner 206 high temperature heat conductive oil mixing after enter into reformer 202, after vaporizer 201 carries out heat exchange, conduction oil after cooling reaches suitable temperature and returns in conduction oil storage device 102, recycles.
Claims (9)
1. a closed-type fuel cell hydrogen source system, it is characterised in that: described 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 production units by carbinol system；
Wherein: hydrogen production units by carbinol includes combustion evaporator processed, reformer, burner, carbon monoxide selective oxidizing reaction device and other aid systems；The general module of burner, reformer, vaporizer and CO selective oxidation reaction device；
Described methanol feeding mechanism, liquid oxygen apparatus connect with the entrance of hydrogen production units by carbinol；Conduction oil stocking system connects with the entrance and exit of hydrogen production units by carbinol；Carbon dioxide storage device, aqueous water storage device connect with the entrance and exit of hydrogen from methyl alcohol respectively.
2. the closed-type fuel cell hydrogen source system described in claim 1, it is characterised in that: other described aid systems include heat conduction oil circulating pump, conduction oil cooler, compressor, depurator and hydrogen gas mixture surge tank；
Conduction oil is entered into after CO selective oxidation reaction device mixes with the high temperature heat conductive oil entering into burner from conduction oil conservation tank by heat conduction oil circulating pump and returns to conduction oil storage tank through reformer, vaporizer and cooler；Depurator is mainly connected with outlet and the hydrogen gas mixture surge tank of CO selective oxidation reaction device.
3. the closed-type fuel cell hydrogen source system described in claim 1, it is characterized in that: described burner is the modular construction of heat exchange form, the gentle body portion of conduction oil is separated by the dividing plate of heat conductivity respectively, and the form of its heat conduction baffle can be that plate-fin structure, sleeve be finned, metal beehive and tubular heat exchanger formula etc. are a kind of or above-mentioned several assembly；Modular burner adopts Flange joint each other.
4. the closed-type fuel cell hydrogen source system described in claim 3, it is characterised in that: the burner side of described modular construction comprises combustion catalyst.
5. the closed-type fuel cell hydrogen source system described in claim 1, it is characterized in that: described reformer is the modular structure of heat exchange form, the gentle body portion of conduction oil is separated by the dividing plate of heat conductivity respectively, and the form of its heat conduction baffle can be that plate-fin structure, sleeve be finned, metal beehive and tubular heat exchanger formula etc. are a kind of or above-mentioned several assembly；Modular burner adopts Flange joint each other.
6. the closed-type fuel cell hydrogen source system described in claim 5, it is characterised in that: modular reformer side comprises methanol-water reforming catalyst.
7. the closed-type fuel cell hydrogen source system described in claim 1, it is characterized in that: be made up of conduction oil side and methanol water mix-ture flow side inside vaporizer, both sides are separated by the dividing plate of heat conductivity respectively, and the form of heat conductivity dividing plate can be that plate-fin structure, sleeve be finned, the finned metal beehive of tubulation and tubular heat exchanger formula etc. are a kind of or above-mentioned several assembly；Wherein preferably plate-fin structure, sleeve is finned, tubulation is finned；Vaporizer adopts modular structure equally, each other and and reformer between adopt Flange joint.
8. the closed-type fuel cell hydrogen source system described in claim 1, it is characterised in that: a heat exchanger is set between reformer and carbon monoxide selective oxidizing reaction device；The outlet of heat exchanger and heat conduction oil circulating pump, the import of burner combustion side, reformer reforms side outlet, CO selects the import of performance oxidation reactor to be connected.
9. the closed-type fuel cell hydrogen source system described in claim 1, it is characterised in that: the both sides of carbon monoxide selective oxidizing reaction device are separated by thermal insulation board；The form of heat conductivity dividing plate can be plate-fin structure, sleeve is finned, tubulation is finned, metal beehive and tubular heat exchanger formula etc. are a kind of or above-mentioned several assembly；Wherein preferably plate-fin structure, sleeve is finned, tubulation is finned；CO selective oxidation reaction device adopt modular structure, each other and and other heat exchangers between adopt Flange joint.
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| CN106898794A (en) * | 2017-04-20 | 2017-06-27 | 武汉理工大学 | A kind of electricity-generating method and TRT based on methanol steam reforming system |
| CN109273745A (en) * | 2018-10-29 | 2019-01-25 | 浙江氢谷新能源汽车有限公司 | Integrated fuel battery device for pure electric automobile |
| CN109546189A (en) * | 2018-10-29 | 2019-03-29 | 南京航空航天大学 | It is a kind of to reform electricity generation system by the multistage of fuel cell hydrogen source of liquid fuel |
| CN110040685A (en) * | 2019-04-29 | 2019-07-23 | 北京铂陆氢能科技开发有限公司 | A kind of liquid organic hydrogen storage material and preparation method |
| CN110649287A (en) * | 2019-09-30 | 2020-01-03 | 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 |
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| CN106898794A (en) * | 2017-04-20 | 2017-06-27 | 武汉理工大学 | A kind of electricity-generating method and TRT based on methanol steam reforming system |
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| CN109546189A (en) * | 2018-10-29 | 2019-03-29 | 南京航空航天大学 | It is a kind of to reform electricity generation system by the multistage of fuel cell hydrogen source of liquid fuel |
| 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 |
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| CN110040685A (en) * | 2019-04-29 | 2019-07-23 | 北京铂陆氢能科技开发有限公司 | A kind of liquid organic hydrogen storage material and preparation method |
| 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 |
| CN110649287A (en) * | 2019-09-30 | 2020-01-03 | 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 |
| CN116979107A (en) * | 2023-09-25 | 2023-10-31 | 成都岷山绿氢能源有限公司 | Fuel cell system |
| CN116979107B (en) * | 2023-09-25 | 2023-12-19 | 成都岷山绿氢能源有限公司 | Fuel cell system |
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