CN1217440C - Hydrogen generating equipment and fuel cell system - Google Patents
Hydrogen generating equipment and fuel cell system Download PDFInfo
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- CN1217440C CN1217440C CN021589836A CN02158983A CN1217440C CN 1217440 C CN1217440 C CN 1217440C CN 021589836 A CN021589836 A CN 021589836A CN 02158983 A CN02158983 A CN 02158983A CN 1217440 C CN1217440 C CN 1217440C
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A hydrogen generation apparatus has a reformer of generating a reformed gas containing at least hydrogen and carbon monoxide by making a material containing an organic compound react with water; carbon-monoxide-removing means of including at least a shifter of reducing the carbon monoxide contained in the reformed gas generated by the reformer in accordance with a shift reaction; and material-humidifying means of humidifying the material by directly or indirectly using moisture contained in the reformed gas.
Description
Technical field
The present invention relates to a kind of hydrogen generation apparatus by reformation such as the fuel based on the fuel of hydrocarbon generation reformation combustion gas, and the fuel cell system or the similar system that use this kind hydrogen generation apparatus.
Background technology
Can be effectively utilized owing to use the fuel cell power generation system of fuel cell to have the heat that is produced in higher electric power formation efficiency and the electric power generative process, therefore can expect using this system aspect family expenses heat energy and the generating.
Under the situation of family expenses, the useful life of the frequent starting of slave unit/stop, equipment and belt-tightening viewpoint, the fuel cell power generation system preferably is operated under the lower temperature.Therefore, developed a kind of high molecular fuel battery, it uses polyelectrolyte membrane to generate parts as its electric power.
Most fuel cells use hydrogen to act as a fuel and generate electric power.Yet, because there is not gas reformation infrastructure at present, so power generation system not only uses fuel cell, also use the hydrogen generation apparatus that reformer is provided, this reformer is by making alcoholic content such as hydrocarbon components such as natural gas or LPG, methyl alcohol and naphtha become to grade raw material and water react and generate the reformation combustion gas that comprises hydrogen.
In the reformation combustion gas that reformer generates, not only include hydrogen, also include carbon dioxide and carbon monoxide as accessory ingredient.Because the high molecular fuel battery developed is operated on 100 degrees centigrade or the lower temperature, thus must minimize the carbon monoxide that is comprised in the reformation combustion gas, to keep the battery electrode activity of such catalysts.Therefore, hydrogen generation apparatus has a kind of like this configuration, and it not only uses the reformer that generates the reformation combustion gas, also uses the carbon monoxide that is made of the purifying part that makes carbon monoxide and water carry out the converter of transformationreation and oxidizing carbon monoxide to remove parts.
Along with the heat that reformer is heated to the required temperature of reforming reaction increases, the efficient of hydrogen generation apparatus further worsens.
Hydrogen generation apparatus makes raw material and steam reactions such as hydrocarbon.Yet, because glassware for drinking water has great gasification latent heat, so reformer needs very many heats to make aqueous vaporization.Therefore, be difficult to the efficient of hydrogen generation apparatus is brought up to a particular value or higher.
On the other hand, because transformationreation is a kind of exothermic equilibrium reaction, along with the raising of the ratio of steam and reformation combustion gas at a lower temperature, the converter that carries out transformationreation that is positioned at the reformer downstream is easier to reduce carbon monoxide, and can reduce the air capacity of required supply response in being in converter downstream purification parts.Therefore, can control the luxus consumption of hydrogen, the work of the line stabilization of going forward side by side.By increasing steam vapour amount and improving temperature, because the raising of transformationreation speed might further reduce the converter volume by reducing catalyst volume.
Yet, because the steam in the converter obtains by reformer, and in order to improve steam vapour amount as described above, need a large amount of gasification latent heats, so the required heat of heated reformate device has increased, and in order to improve transducer effciency and to reduce piece volumes and the steam vapour amount that increases in the reformer makes reformer efficiency lower.
In order to prevent the generation of above-mentioned situation, a kind of like this technology has been proposed, it adds to by the water that will prepare separately and carries out humidification (for example, referring to Japanese patent application publication No. No.10-330101 and Japanese patent application publication No. No.11-106204) in the raw material combustion gas.Therefore,, might reduce the required heat of reformer apparatus, and improve the efficient of transformationreation in the converter owing to reduced the gasification latent heat that water is become steam.In addition, remove the heat of parts or fuel cell cooling water, might under situation about not lowering efficiency, carry out humidification by using carbon monoxide.
Yet a kind of raw material combustion gas that is used for conventional hydrogen generation apparatus only comes humidification by a thermal source that uses maker.Therefore, the raising that will produce efficient is restricted problem, and makes recuperation of heat and humidification stringing become complicated.
Summary of the invention
The present invention is implemented the problems referred to above that are used to solve conventional hydrogen generation apparatus, its objective is provides a kind of efficient operation, and simultaneously with the hydrogen generation apparatus of simple structure and lower heat humidify raw material combustion gas, and a kind of fuel cell power generation system that uses this hydrogen generation apparatus.
The 1st invention of the present invention is a kind of hydrogen generation apparatus, comprising:
Reformer, it generates the reformation combustion gas that comprises hydrogen and carbon monoxide at least by making the raw material include organic compounds and water react;
Carbon-monoxide-removing means comprises the converter of described carbon monoxide contained in the described reformation combustion gas that a kind of minimizing generates according to the described reformer of transformationreation at least; And
The raw material damping device, it comes the described raw material of humidification by using the aqueous vapor that is comprised in the described reformation combustion gas,
Wherein, described raw material damping device is by using the described raw material of aqueous vapor humidification that is comprised from the reformation combustion gas of described carbon-monoxide-removing means output.The 2nd invention of the present invention is according to the 1st the described hydrogen generation apparatus of invention, wherein said raw material damping device has and sees through the saturating film of water of aqueous vapor at least, and provides the saturating film of described water to make to form the border between the path of the path of described reformation combustion gas and described raw material.
The 3rd invention of the present invention is that the saturating film of wherein said water also sees through hydrogen according to the 2nd the described hydrogen generation apparatus of invention.
The 4th invention of the present invention is that wherein said raw material damping device makes between described reformation combustion gas and the described raw material and carries out heat exchange according to the 2nd the described hydrogen generation apparatus of invention.
The 5th invention of the present invention is a kind of fuel cell power generation system, comprising:
As the 1st the described a kind of hydrogen generation apparatus of invention; And
Fuel cell is used for generating electric power by the reformation combustion gas that provides from described hydrogen generation apparatus.
The 6th invention of the present invention is a kind of method for forming hydrogen, comprising:
Reforming step is used for generating the reformation combustion gas that comprises hydrogen and carbon monoxide at least by making the raw material include organic compounds and water react;
Carbon monoxide is removed step, comprises a kind of shift step that is used for reducing according to transformationreation the described carbon monoxide in the reformation combustion gas that described reforming step generates at least; And
Raw material humidification step is used for coming the described raw material of humidification by the aqueous vapor of using described reformation combustion gas to comprise,
Wherein, described raw material humidification step is by using the described raw material of aqueous vapor humidification that is comprised from the reformation combustion gas of described carbon-monoxide-removing means output.
Description of drawings
Fig. 1 is the signal longitdinal cross-section diagram that shows the fuel cell power generation system configuration of the embodiment of the invention 1.
Fig. 2 (a) is the signal longitdinal cross-section diagram that shows the fuel cell power generation system configuration of the embodiment of the invention 2.
Fig. 2 (b) is the signal longitdinal cross-section diagram that the raw material humidifying component of the fuel cell power generation system of the demonstration embodiment of the invention 2 disposes.
Fig. 3 is the signal longitdinal cross-section diagram that shows the fuel cell power generation system configuration of the embodiment of the invention 3.
Fig. 4 is the signal longitdinal cross-section diagram that shows the fuel cell power generation system configuration of the embodiment of the invention 4.
Fig. 5 is the signal longitdinal cross-section diagram that shows the fuel cell power generation system configuration of the embodiment of the invention 5.
Fig. 6 is the signal longitdinal cross-section diagram that the raw material humidifying component of the fuel cell power generation system of the demonstration embodiment of the invention 6 disposes.
Fig. 7 is the signal longitdinal cross-section diagram that the raw material humidifying component of the fuel cell power generation system of the demonstration embodiment of the invention 7 disposes.
Denotational description
1... reformer
2... heater block
3... raw material provides parts
4... reformation water supply component
5...CO converter
6... air provides parts
7...CO purifying part
8... fuel cell power generates parts
9,69... raw material humidifying component
10... cooling water circulation member
11... cooling water temperature detection part
12... combustion gas provides parts
30,40, the total heat-exchanging part of 50...
Provide parts 51... become water
71... humidification water temperature detection part
Embodiment
Embodiments of the invention are described below with reference to the accompanying drawings.
(embodiment 1)
Below at first by describe a kind of configuration of the fuel cell power generation system of present embodiment with reference to figure 1.Fig. 1 is the schematic section that shows a kind of hydrogen generation apparatus configuration of present embodiment.
Among Fig. 1, reference number 1 expression reformer, the heater block of 2 expression heated reformate devices, the supply raw materials raw material of reformer 1 of 3 expressions provides parts, and 4 expressions provide the reformation water supply component of water to reformer.Reformer 1 raw material provides parts 3 and reformation water supply component to constitute reformer of the present invention.Be set at the downstream of reformer corresponding to the CO converter 5 of converter of the present invention, air provides parts 6 and is set at the downstream of CO converter 5 corresponding to the CO purifying part 7 of carbon-monoxide-removing means of the present invention.CO converter 5 and CO purifying part 7 have constituted carbon-monoxide-removing means of the present invention.Fuel cell power generation parts 8 corresponding to fuel cell of the present invention are set at CO purifying part 7 downstreams.Reference number 9 expressions are corresponding to the raw material humidifying component of raw material damping device of the present invention, and 10 expressions are used for generating by fuel cell power the cooling water circulation member of parts 8 recirculated cooling waters.Temperature as the cooling water of hydro-thermal supporting body of the present invention is detected by cooling water temperature detector 11.Reference number 12 expressions are used to provide combustion gas to provide parts to the combustion gas of heater block.Be received in reformer 1 by Ru being added the reforming catalyst that obtains in the aluminium oxide, the reforming catalyst of being made by copper and zinc is received in CO converter 5, is received in CO purifying part 7 by Pt being added the CO cleaning catalyst that obtains in the aluminium oxide.These catalyst are the catalyst that are normally used for hydrogen generation apparatus.Even use other catalyst, also can not change advantage of the present invention with identical function.For example, the Ni catalyst can be used as reforming catalyst, and Pt catalyst or Fe-Cr catalyst can be used as the CO conversion catalyst, and Ru catalyst etc. can be used as the CO cleaning catalyst.
Next, the running of various details fuel cell power generation system.
The raw material that is provided for reformer 1 is comprised natural gas, methyl alcohol and gasoline, and the reformation type comprises steam reforming that is undertaken by interpolation steam and the part reformation of being undertaken by the interpolation air.To describe below by obtain a kind of situation of reformation combustion gas with the steam reforming natural gas.
The natural gas of one of raw material provides parts 3 to be provided to reformer 1 from raw material.Water is provided to reformer 1 from reformation water supply component 4, and is gasificated into steam in reformer 1.Steam mixes in raw material, and make it with insert reformer 1 in reforming catalyst contact.
Reforming catalyst is heated, and makes it to have the temperature near 700 degree Celsius, allows raw material and steam react, and converts the reformation combustion gas that mainly comprises hydrogen to.Although the composition of the reformation combustion gas that generates depends on the temperature of reforming catalyst slightly, except that steam, the reformation combustion gas comprises mean value respectively and is about 80% hydrogen, 10% carbon dioxide and 10% carbon monoxide.By the transformationreation in the CO converter that is arranged on reformer 1 downstream, the CO concentration of reformation combustion gas is reduced to and is about 0.5%, and then by making the airborne oxygen and the CO that provide parts 6 to provide from purifying air react, this concentration further is reduced to 10ppm or lower.
Therefore, the reformation combustion gas that does not comprise CO is provided for fuel cell power and generates parts 8.Because when generating electric power, heat and electric power generate simultaneously, so will generate parts 8 with the water quench fuel cell power that cooling water circulation member 10 provides to keep stationary temperature.Fuel cell power generates the temperature of parts 8 and controls by the increase and decrease cooling water inflow, so cooling water temperature detector 11 detected temperature become constant.
Cooling water through heating is sent to raw material humidifying component 9, and the raw material that humidification provides parts 3 to provide from raw material is provided.Raw material humidifying component 9 carries out work, makes raw material fully contact with water, the dew point temperature humidify raw material on cooling water temperature.Humidify raw material is provided to reformer 1.Because cooling water temperature is set to 65 degrees centigrade to 90 degrees centigrade usually, fuel cell power generates parts 8 and demonstrates higher characteristic in this temperature range, after through raw material humidifying component 9, S/C (ratio of carbon in steam and the raw material) is about 0.5 to 2.In addition, reformation water supply component 4 also provides water extraly, makes S/C scope in the reformer between 2.5 to 3.5.When cooling water temperature is elevated to a certain degree, need provide parts 4 to provide water from reformation water to reformer 1, be possible because the essential water yield is mixed with raw material.In addition, corresponding situation also may comprise when the water yield that adds humidity and control and provide parts 4 additionally to provide from the reformation coolant-temperature gage of calculating raw material when the cooling water temperature that detects according to cooling water temperature detector 11 changes the temperature of fuel cell power generation parts 8, starting device or situation about working on.
Next, the operation principle of this embodiment will be described below.Although from general family to the demand balanced perspective between electric power and the heat, use the associating generation system of fuel cell power generation system also to use the heat of following power production process to produce effectively, but still need to improve power ratio, that is, and the electric power formation efficiency.In order to improve the electric power formation efficiency, the essential efficient that improves hydrogen generation apparatus.Therefore, effectively utilize the exhaust gas heat of heated reformate device combustion component usually, perhaps the loss of the heat that discharges from hydrogen generation apparatus.
Yet,, need bigger heat exchange area in order to reclaim cryopumping heat.Because this makes the volume of equipment increase, be difficult to efficient is brought up to certain level or higher.Especially, according to reforming reaction, with the glassware for drinking water of raw material reaction a large amount of gasification latent heats is arranged, thereby this has stoped the further raising of efficient.In addition, fuel cell power generates parts and carries out work usually like this, makes the heat that produces when generating electric power with water quench keep its steady temperature of 65 degrees centigrade to 90 degrees centigrade.This heat is normally used for providing hot water.
On the other hand, because making, this embodiment fuel cell power may be generated the humidification that some heat that produces in the parts 8 is used for raw material, and take out some required steam of reformer 1, therefore may control the heat value that is used to evaporate the water that is provided to hydrogen generation apparatus.In order under atmospheric pressure, water to be evaporated the temperature that needs are 100 degrees centigrade or higher effectively.Yet, by making raw material contact with the water that is lower than 100 degrees centigrade, may reclaim the heat that comes from low-temperature heat source (generating parts 8) effectively, obtain steam with heat value effectively, and improve the efficient of hydrogen generation apparatus less than the situation of evaporation water as fuel cell power.
This embodiment uses has a kind of like this configured parts as raw material humidifying component 9, and these parts have the structure by the water tank recycle feed combustion gas of storage cooling water.Yet, can use any device as raw material damping device of the present invention, as long as this device has and can make cooling water and the contacted configuration of raw material combustion gas effectively.In addition, can also use and to allow by carrying out heat exchange and the contacted configuration of heated water and raw material with cooling water.In addition, hydro-thermal supporting body of the present invention is described as the cooling water that the direct image raw material provides heat and aqueous vapor.Yet, also may replace thermal medium such as spent glycol and add hot water, and with the water humidify raw material after the heating.At this moment, thermal medium provides heat and aqueous vapor to raw material indirectly.
In addition, fuel cell power generates parts 8 normally by clamping the polymer electrolyte electrolyte with the plate electrode of the carbon that is covered with the carrying noble metal, separating and roll that they form with carbon or metal isolator.In the situation of this embodiment, although parts 8 are constructed such that by form cooling-water duct and recirculated water on above-mentioned isolator, also cooling segment can be built into the feasible heat that electrode generated that can remove fuel cell power generation parts 8 effectively.
(embodiment 2)
Next, various details embodiment 2.Shown in Fig. 2 (a), this embodiment and embodiment 1 are similar, generate parts 8 downstreams except the total heat exchanger 30 corresponding to raw material damping device of the present invention is provided at fuel cell power.Therefore, present embodiment is described in main just different with embodiment 1 place, in Fig. 2 (a), provide identical identifier and omit it and describe in detail, therefore an example of hydrogen generation apparatus of the present invention and an example of method for forming hydrogen have been described below for identical with Fig. 1 or corresponding part.
Fig. 2 (a) is the schematic section that shows fuel cell power generation system configuration of the present invention.The reformation combustion gas that hydrogen generation apparatus generated is provided for fuel cell power and generates parts 8, and most of hydrogen is consumed and is used for the electric power generation, and is used as waste gas release.Because waste gas still comprises hydrogen, thus heater block 2 itself and the heating fuel that provides parts 12 to provide from combustion gas are burnt together, with heated reformate device 1.
Owing in waste gas, comprise a large amount of steam, the temperature of flame and the efficient of reformer 1 therefore when direct burnt gas in heater block 2, have been reduced.
Yet in the situation of this embodiment, waste gas carries out heat exchange fully with the raw material that provides parts 3 to provide from raw material total heat-exchanging part 30.In addition, shown in Fig. 2 (b), because the saturating film 30a of water that is used for isolating waste gas and raw material and forms the border between exhaust path and the feedstock pathway is formed in total heat-exchanging part 30, so the steam in the waste gas passes the saturating film 30a of water and is transferred to raw material, with humidify raw material.
Therefore,, may reduce the water yield that provides parts 4 to be provided to reformer 1 from reformation water by humidify raw material and a part of steam that is used for being undertaken reforming reaction of acquisition by raw material, and the heat value of control reformer 1.In addition, owing to the steam that is included in the waste gas is removed simultaneously, and prevent that therefore the flame temperature in the heater block 2 from reducing, so the efficient of hydrogen generation apparatus is further improved.
Although this embodiment makes the saturating film of water as the dielectric film that sees through film and be used for high molecular fuel battery of the present invention, also can use any film, as long as this film allows water to see through (as the saturating film of macromolecule water).Even under the situation of using materials such as zeolite formation film that can be permeable, also can obtain same effect.
(embodiment 3)
Next, various details embodiment 3.As shown in Figure 3, embodiment 3 and embodiment 2 are similar, except the total heat exchanger 40 corresponding to raw material damping device of the present invention is set between CO purifying part 7 and the fuel cell power generation parts 8.Therefore, present embodiment is described in main just different with embodiment 2 place, in Fig. 3 for identical identifier to be provided and to have omitted its detailed description with the identical or corresponding part of Fig. 2 (a).In addition, total heat exchanger 40 has the saturating film of a water, be used for the reformation combustion gas and the raw material that discharge from CO purifying part 7 are kept apart, and the border between formation reformation combustion gas path and the feedstock pathway.
Fig. 3 is the schematic section that shows the fuel cell power generation system configuration of present embodiment.In the situation of this embodiment, by through the reformation combustion gas after the CO purifying part 7 and raw material carries out total heat exchange and saturating film is transferred to raw material with the steam in the reformation combustion gas by water, total heat-exchanging part 40 humidify raw materials.By humidify raw material, may reduce the water yield that provides from reformation water supply component 4 and the heat value of controlling reformer 1.
In addition, owing to be generally 100 degrees centigrade or higher by the reformation combustion gas after the CO purifying part 7, and this temperature is higher than the working temperature that fuel cell power generates parts 8, therefore may be in the present embodiment by reclaiming steam and the heat that CO purifying part 7 and fuel cell power generate the reformation combustion gas between the parts 8, and the feasible efficient that has not only improved reformer 1, also effectively the reformation fuel gas temperature is reduced to the temperature that fuel cell power generates parts 8, and the ducted water condensation between control CO purifying part 7 and the fuel cell power generation parts 8.
(embodiment 4)
Next, various details embodiment 4.As shown in Figure 4, embodiment 4 and embodiment 2 are similar, and except total heat exchanger 50 is arranged between CO converter 5 and the CO purifying part 7, and the water that becomes that is provided with the CO converter 5 that is used to supply water in the upstream of CO converter 5 provides parts 51.Therefore, below will be main just different places with embodiment 2 embodiment 4 is described, in Fig. 4 for identical identifier to be provided and to have omitted its detailed description with the identical or corresponding part of Fig. 2 (a).In addition, be similar to the situation of total heat exchanger 30 and 40, total heat exchanger 50 has the saturating film of a water, be used for the reformation combustion gas and the raw material that discharge from CO converter 5 are kept apart, and the border between formation reformation combustion gas path and the feedstock pathway.
Fig. 4 is the schematic section that shows the fuel cell power generation system configuration of present embodiment.
In the situation of embodiment 3, the steam and the heat that are comprised in the reformation combustion gas are recovered in the downstream of CO purifying part 7.Yet, in the steam vapour amount in increasing converter, trouble has just produced, the reaction that is arranged in converter downstream purification parts is because excessive steam and deterioration, and the electric power formation efficiency also might be by deterioration, become excessive because be arranged in the steam vapour amount of the fuel cell power generation parts in purifying part downstream, so water is easy in the electrode surface condensation.
Yet, in the example of present embodiment, by total heat exchanger 50 heat exchange fully, come humidify raw material by the steam in the reformation combustion gas being transferred to raw material via the saturating film of water by the raw material after the CO converter 5 and reformation combustion gas.Yet, because after passing through CO converter 5, reclaimed steam and heat from the reformation combustion gas, therefore the reaction that may prevent CO purifying part 7 prevents perhaps that owing to deterioration takes place excessive steam water condensation from generating on the electrode surface of parts 8 at fuel cell power.Therefore may under the situation that does not make the efficient of hydrogen generation apparatus reduce, reduce the volume of CO converter, and stably reduce CO concentration.
This embodiment uses total heat exchanger 50 as raw material damping device of the present invention.Yet, also can use any configuration, as long as this configuration makes it can reclaim aqueous vapor from the reformation combustion gas of CO converter 5 outputs.For example, can also use a kind of method of from water, separating combustion gas by cooling reformation combustion gas.Containing by reformation water supply component 4 in the reformation combustion gas and becoming water provides parts 51 to provide condensation aqueous vapor in water and the reformation combustion gas to reformer 1 and CO converter 5.In addition, can also use and do not comprise and become the configuration that water provides parts 51.
(embodiment 5)
Next, various details embodiment 5.As shown in Figure 5, embodiment 5 is identical with embodiment 1, provides between parts 3 and the reformer 1 except the raw material humidifying component 69 that stores the water that heats with sunlight is set at raw material here.Therefore, below will be main just different places with embodiment 1 embodiment 5 is described, in Fig. 5, identical identifier is provided and has omitted its detailed description for identical with Fig. 1 or corresponding part.
Fig. 5 is the schematic section that shows the fuel cell power generation system configuration of present embodiment.Although embodiment 1 adds hot water by the heat that uses fuel cell power to generate parts 8 in raw material humidifying component 9, also can produce trouble, the hot water service efficient of promptly using fuel cell power to generate the used heat of parts 8 has reduced.
Yet, in the situation of present embodiment, may be not making the efficient that improves reformer 1 under the situation of hot water service efficient step-down effectively, because the water in the raw material humidifying component 69 heats with sunlight.
By using geothermal resources such as hot spring to replace sunlight also can obtain identical effect.
(embodiment 6)
Next, various details embodiment 6.Embodiment 6 and embodiment 2 are similar, and except replace having the total heat exchanger 30 of the saturating film 30a of water with raw material humidifying component 80, this raw material humidifying component 80 uses the water hydrogen that can see through hydrogen to see through film.Therefore, below will be main just different places with embodiment 2 embodiment 6 is described, and the detailed description of omission same section.
Fig. 6 is the schematic section of raw material humidifying component 80 of the fuel cell power generation system of present embodiment, and the water hydrogen that wherein can see through aqueous vapor and hydrogen sees through film 81 and is formed on the position that the saturating film 30a of water is provided.
In the situation of embodiment 2, by with the saturating film 30a of the water in total heat-exchanging part 30 water gas shift in the waste gas being come humidify raw material, and the hydrogen of total event is provided for heater block 2 in the waste gas.Yet, in the situation of present embodiment, owing to see through film 81 and a part of hydrogen in the waste gas returned to raw material by making waste gas see through water hydrogen, therefore fuel cell power may be generated in the parts 8 unreacted hydrogen and be used for fuel cell power once more and generate, and therefore improve the electric power formation efficiency.
A kind of polymer electrolyte dielectric film that is used for high molecular fuel battery is used as water hydrogen and sees through film 81.It is well-known that the polymer electrolyte dielectric film can see through hydrogen.Yet in fuel cell component, the oxygen that sees through on hydrogen and the negative electrode that does not participate in the electric power generation reacts, and has reduced the electric power formation efficiency, has perhaps damaged film.Therefore, carried out at the various researchs of controlling.In general, lower and film becomes when the dew point of recyclegas, and hydrogen is easier to see through when slightly doing.In the situation of this embodiment, hydrogen is easier to see through, because near unstripped gas the former glassware inlet 84 and near the waste gas the waste gas outlet 83 have lower dew point respectively.Water hydrogen sees through film not only can use the polymer electrolyte dielectric film, can also use zeolite membrane, this film has the aperture that can only see through the hydrogen among carbon dioxide and the hydrogen, use silicon rubber or use hydrophilic compounds such as phosphate are mixed into the film that thermal resistance polymeric membrane such as polyimides obtain.
The actuating force of the saturating film of hydrogen is the pressure differential between the hydrogen local pressure of waste gas and raw material.Therefore, by guaranteeing enough areas of film, just may before disappearing, actuating force (that is the pressure reduction between the hydrogen concentration of film both sides) reclaim hydrogen.But the designer of maker can freely select above-mentioned film from the viewpoint of cost and space setting.
In addition, also alternately provide waste gas and raw material combustion gas both sides,, just may hydrogen and aqueous vapor be recovered to the process of raw material with less volume realization to increase the area that water hydrogen sees through film 81 to each film by the film that reduces pressure.
(embodiment 7)
Various details embodiment 7.As shown in Figure 7, embodiment 7 and embodiment 2 are similar, except the raw material humidifying component 90 corresponding to raw material damping device of the present invention is provided at the downstream that fuel cell power generates parts 8, and raw material humidifying component 90 has the composition identical with the polymer electrolyte electricity fuel cell, promptly all provides the carbon electrode 92 of carrying platinum on the two sides of proton-conductive films 91.Therefore, below will be main just different places with embodiment 2 this embodiment is described, and the detailed description of omission same section.
Fig. 7 is the schematic section of raw material humidifying component 90 of the fuel cell power generation system of present embodiment.Be arranged with on the proton-conductive films 91 towards the electrode 92a of exhaust flow with towards the electrode 92b of raw material gas-flow, it is provided on the position of the saturating film 30a of water.Electrode 92a and 92b are connected to external voltage controller 93 to generate electrical potential difference according to the voltage that applies from voltage controller 93 raw material humidifying component 90.In the superincumbent configuration, proton-conductive films 91 is examples of hydrophilic proton conduction body, and electrode 92a, 92b and voltage controller 93 are as voltage bringing device of the present invention.
Yet this embodiment comes through the hydrogen in the waste gas by apply voltage on electrode 92a that is arranged at proton-conductive films 91 both sides and 92b.Therefore, can Be Controlled owing to see through the amount of hydrogen, and hydrogen ion is being followed hydrone and moved, so more effectively permeate water and hydrogen.At this moment, the electrical potential difference between electrode 92a and the 92b is configured such that the electromotive force of electrode 92b is higher than the electromotive force of electrode 92a.
Being made up of hydrogen electrode (reformation combustion gas electrode) and oxygen electrode (air electrode) although have the polymer electrolyte electricity fuel cell of the configuration that is similar to raw material humidifying component 90, in the situation of this embodiment, is recycle feed gas rather than oxygen at the oxygen electrode end.Unstripped gas does not work as oxidant, but has and inert gas identical functions such as nitrogen.That is, hydrogen is separated by hydrogen electrode and is become ion, and these ions pass through film, and is combined into hydrogen molecule once more at the unstripped gas termination electrode.Because 90 of raw material humidifying components depend on the working of concentration cell of two interelectrode hydrogen concentration differences, so hydrogen moves by short circuit two electrodes.In addition, by applying voltage, may increase the displacement of hydrogen.
In addition, when the heater block 2 that is used for heated reformate device 1 is provided at waste gas outlet 83 downstreams, may control the temperature of reformer 1 by the transmission rates of control hydrogen.Can control the transmission rates of hydrogen by control will be applied to the electrode 92a that is arranged on proton-conductive films 91 both sides and the voltage on the 92b according to above-mentioned principle.
[example]
(example 1)
In the situation of the fuel cell power generation system of Fig. 1, the Ru catalyst of 0.2L is added into reformer 1, and the copper-zinc catalyst of 2L is added into CO converter 5, and the Pt catalyst of 0.2L is added into CO purifying part 7.Provide methane that parts 3 provide by raw material humidifying component 9 humidifications with the speed of 7L/min from raw material, in addition, reformation water supply component 4 adds water makes S/C become 3 they are provided to reformer 1.The fuel value of adjusting heater block 2 makes the Ru catalyst in the reformer 1 become 700 degrees centigrade, generating the reformation combustion gas, and this combustion gas is offered fuel cell power generates parts 8.Fuel cell power generates parts 8 generation electric power makes DC power become 2 kilowatts.Can obtain 37% electric power formation efficiency, this be by regulate cooling water flow make cooling water temperature detection part 11 detected temperature become 80 degrees centigrade, and calculate according to the DC power meter that offers raw material and provide the methane gross calorific value of parts 3 and heater block 2 and 2 kilowatts.
(example 2)
In the situation of the fuel cell power generation system of Fig. 2, be similar to the situation of example 1, in reformer 1, CO converter 5 and CO purifying part 7, add catalyst respectively.Provide methane that parts 3 provide by total heat-exchanging part 30 humidifications with the speed of 7L/min from raw material, in addition, reformation water supply component 4 adds water makes S/C become 3 they are provided to reformer 1.The fuel value of adjusting heater block 2 makes the Ru catalyst in the reformer 1 become 700 degrees centigrade, generating the reformation combustion gas, and this combustion gas is offered fuel cell power generates parts 8.Fuel cell power generates parts 8 generation electric power makes DC power become 2 kilowatts.Can obtain 38% electric power formation efficiency, this is to provide the methane gross calorific value of parts 3 and heater block 2 and 2 kilowatts DC power meter to calculate according to offering raw material.
(example 3)
In the situation of the fuel cell power generation system of Fig. 3, be similar to the situation of example 1, in reformer 1, CO converter 5 and CO purifying part 7, add catalyst respectively.Provide methane that parts 3 provide by total heat-exchanging part 40 humidifications with the speed of 7L/min from raw material, in addition, reformation water supply component 4 adds water makes S/C become 3 they are provided to reformer 1.The fuel value of adjusting heater block 2 makes the Ru catalyst in the reformer 1 become 700 degrees centigrade, generating the reformation combustion gas, and this combustion gas is offered fuel cell power generates parts 8.Fuel cell power generates parts 8 generation electric power makes DC power become 2 kilowatts.Can obtain 38.5% electric power formation efficiency, this is to provide the methane gross calorific value of parts 3 and heater block 2 and 2 kilowatts DC power meter to calculate according to offering raw material.
(example 4)
In the situation of the fuel cell power generation system of Fig. 4, the copper-zinc catalyst of 1L is added CO converter 5.In reformer 1 and CO purifying part 7, add respectively and the catalyst of the situation equal quantities of example 1.Provide methane that parts 3 provide by total heat-exchanging part 50 humidifications with the speed of 7L/min from raw material, in addition, reformation water supply component 54 adds water makes S/C become 3 they are provided to reformer 1.The fuel value of adjusting heater block 2 makes the Ru catalyst in the reformer 1 become 700 degrees centigrade, to generate the reformation combustion gas.The water that becomes in CO converter 5 upstreams provides parts 51 that water is provided, and makes S/C become 5.Fuel cell power generates parts 8 generation electric power makes DC power become 2 kilowatts.Can obtain 39% electric power formation efficiency, this is to provide the methane gross calorific value of parts 3 and heater block 2 and 2 kilowatts DC power meter to calculate according to offering raw material.
(example 5)
In the situation of the fuel cell power generation system of Fig. 5, similar with the situation of example 1, provide methane that parts 3 provide by raw material humidifying component 69 humidifications with the speed of 7L/min from raw material, and be provided for reformer 1.Raw material humidifying component 69 is coated with black, makes it expose in the sun fully.Show that with the water temperature result in the raw material humidifying component 69 of humidification water temperature detection part 71 measurements water temperature is 93 degrees centigrade.As the result who measures by the steam vapour amount in the gas after the raw material humidifying component 69, S/C is shown as 3.1.Therefore, no longer add water to reformation water supply component 4.The fuel value of adjusting heater block 2 makes the Ru catalyst in the reformer 1 become 700 degrees centigrade, generating the reformation combustion gas, and this combustion gas is offered fuel cell power generates parts 8.Fuel cell power generates parts 8 generation electric power makes DC power become 2 kilowatts.Can obtain 41% electric power formation efficiency, this is to provide the methane gross calorific value of parts 3 and heater block 2 and 2 kilowatts DC power meter to calculate according to offering raw material.
(example 6)
In the situation of the fuel cell power generation system of Fig. 2, be similar to the situation of example 1, in reformer 1, CO converter 5 and CO purifying part 7, add catalyst respectively.Be provided with raw material humidifying component 80 shown in Figure 6 to replace total heat-exchanging part 30.Provide methane that parts 3 provide by raw material humidifying component 80 humidifications with the speed of 7L/min from raw material, in addition, reformation water supply component 4 adds water makes S/C become 3 they are provided to reformer 1.The fuel value of adjusting heater block 2 makes the Ru catalyst in the reformer 1 become 700 degrees centigrade, to generate the reformation combustion gas, this combustion gas is offered fuel cell power generate parts 8, and make parts 8 generate electric power.Can obtain 41.5% electric power formation efficiency, this is to provide the methane gross calorific value of parts 3 and heater block 2 and the DC power meter of generation to calculate according to offering raw material.
(example 7)
In the situation of the fuel cell power generation system of Fig. 2, be similar to the situation of example 1, in reformer 1, CO converter 5 and CO purifying part 7, add catalyst respectively.Be provided with raw material humidifying component 90 shown in Figure 7 to replace total heat-exchanging part 30.Provide methane that parts 3 provide by raw material humidifying component 80 humidifications with the speed of 7L/min from raw material, in addition, reformation water supply component 4 adds water makes S/C become 3 they are provided to reformer 1.The fuel value of adjusting heater block 2 makes the Ru catalyst in the reformer 1 become 700 degrees centigrade, to generate the reformation combustion gas, this combustion gas is offered fuel cell power generate parts 8, and make parts 8 generate electric power.Apply 200 millivolts voltage being positioned on electrode 92a on proton-conductive films 91 two sides and the 92b.Can obtain 42% electric power formation efficiency, this is to provide the methane gross calorific value of parts 3 and heater block 2 and the DC power meter of generation to calculate according to offering raw material.
(comparative example 1)
In the situation of example 1, the methane that provides parts 3 to provide from raw material with the speed of 7L/min is provided directly to reformer 1, and without raw material humidifying component 9 humidification methane.Similar with the situation of example 1, fuel cell power generates parts 8 generation electric power makes DC power become 2 kilowatts.The flow of regulating cooling water makes cooling water temperature detection part 11 detected temperature become 80 degrees centigrade.Can obtain 33% electric power formation efficiency, this is to provide the methane gross calorific value of parts 3 and heater block 2 and 2 kilowatts DC power meter to calculate according to offering raw material.
Each top embodiment is described as and comprises that fuel cell power generates the fuel cell power generation system of parts 8.Yet, can also not comprise that the single hydrogen generation apparatus of fuel cell power generation parts 8 is realized the present invention.
In addition, in the situation of each embodiment, the fuel cell power generation system has formed a circulation in the above,, the waste gas that discharges from fuel cell power generation parts 8 is provided to the heater block 2 of reformer 1 that is.Yet, can also be used for other external device (ED) with generate the waste gas that parts 8 discharge from fuel cell power, and fuel cell power generation system of the present invention needn't form the circulation of closing of any kind of, with any gas and the raw material of circulating.
In addition, in the above among each embodiment, humidify raw material be from reformer 1 directly output the reformation combustion gas or from the waste gas of fuel cell power generation system 8 outputs, but of the present inventionly be not limited to this composition.That is to say that the raw material damping device of indirect humidify raw material can use other gas the reformed gas of directly exporting except the reformer from the fuel cell power generation system 1 to come humidify raw material in the present invention.
In addition, in the situation of example 5, suppose that external device (ED) of the present invention is a raw material humidifying component 69 in the above, heat offers it with the form of sunlight or underground heat.Yet external device (ED) is not limited to parts 69.That can also use that boiler and refrigerator etc. are independent of the fuel cell power generation system provides the system of thermal source and watering as raw material.
As mentioned above, according to the present invention, the required heat value that evaporates the water can be controlled by reformer.
In addition,, may not only control the required heat value that evaporates the water, can also from waste gas, steam be removed by making that generating parts waste gas and raw material afterwards through fuel cell power carries out heat exchange completely.Therefore may prevent the reduction of flame temperature in the heater block.
In addition, carry out total heat exchange by making through reformed gas and raw material after the CO purifying part, may not only control the required heat value that evaporates the water, can also effectively the temperature of reformed gas be reduced to the working temperature of fuel cell power generation parts, and control the condensation of water in the pipeline simultaneously.
In addition, carry out total heat exchange through reformed gas and raw material after the CO converter, may not only control the required heat value that evaporates the water, can also reduce the volume of CO converter, and stably reduce CO concentration by making.
In addition, by with sunlight heating raw humidifying component, may improve the efficient that hydrogen generates parts, and not reduce the efficient of hot water service.
Therefore, according to the present invention, may provide a kind of fuel cell power generation system with higher power formation efficiency.
As mentioned above,, may improve the efficient of hydrogen generation apparatus, and reduce the catalyst volume of CO converter according to the present invention.
Claims (6)
1. hydrogen generation apparatus comprises:
Reformer, it generates the reformation combustion gas that comprises hydrogen and carbon monoxide at least by making the raw material include organic compounds and water react;
Carbon-monoxide-removing means comprises the converter that reduces described carbon monoxide contained in the described reformation combustion gas of described reformer generation according to transformationreation at least; And
The raw material damping device, it comes the described raw material of humidification by using the aqueous vapor that comprises in the described reformation combustion gas
Wherein, described raw material damping device is by using the described raw material of aqueous vapor humidification that is comprised from the reformation combustion gas of described carbon-monoxide-removing means output.
2. hydrogen generation apparatus according to claim 1 is characterized in that, described raw material damping device has and sees through the saturating film of water of aqueous vapor at least, and provides the saturating film of described water to make to form the border between the path of the path of described reformation combustion gas and described raw material.
3. hydrogen generation apparatus according to claim 2 is characterized in that, the saturating film of described water also sees through hydrogen.
4. hydrogen generation apparatus according to claim 2 is characterized in that, described raw material damping device carries out heat exchange between described reformation combustion gas and described raw material.
5. a fuel cell power generation system is characterized in that, comprising:
Hydrogen generation apparatus as claimed in claim 1; And
Fuel cell is used for generating electric power by the reformation combustion gas that provides from described hydrogen generation apparatus.
6. method for forming hydrogen comprises:
Reforming step is used for generating the reformation combustion gas that comprises hydrogen and carbon monoxide at least by making the raw material include organic compounds and water react;
Carbon monoxide is removed step, comprises the shift step that is used for reducing according to transformationreation the described carbon monoxide in the reformation combustion gas that described reforming step generates at least; And
Raw material humidification step is used for coming the described raw material of humidification by the aqueous vapor of using described reformation combustion gas to comprise,
Wherein, described raw material humidification step is by using the described raw material of aqueous vapor humidification that is comprised from the reformation combustion gas of described carbon-monoxide-removing means output.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001040037A JP2002242989A (en) | 2001-02-16 | 2001-02-16 | Base isolation method and base isolation device |
| JP2001400372 | 2001-12-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1428884A CN1428884A (en) | 2003-07-09 |
| CN1217440C true CN1217440C (en) | 2005-08-31 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN021589836A Expired - Fee Related CN1217440C (en) | 2001-02-16 | 2002-12-27 | Hydrogen generating equipment and fuel cell system |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2002242989A (en) |
| CN (1) | CN1217440C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1505036B1 (en) * | 2003-07-29 | 2010-08-11 | Panasonic Corporation | Hydrogen generator and fuel cell power generation system |
| KR100570754B1 (en) | 2004-02-26 | 2006-04-12 | 삼성에스디아이 주식회사 | Reformer for fuel cell system and fuel cell system having thereof |
| KR20060095109A (en) | 2005-02-28 | 2006-08-31 | 삼성에스디아이 주식회사 | Non-reactive fuel solution apparatus for reformer and fuel cell system with the same |
-
2001
- 2001-02-16 JP JP2001040037A patent/JP2002242989A/en active Pending
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2002
- 2002-12-27 CN CN021589836A patent/CN1217440C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002242989A (en) | 2002-08-28 |
| CN1428884A (en) | 2003-07-09 |
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