CN103588169A - Reforming system and fuel cell system - Google Patents

Reforming system and fuel cell system Download PDF

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Publication number
CN103588169A
CN103588169A CN201310279707.6A CN201310279707A CN103588169A CN 103588169 A CN103588169 A CN 103588169A CN 201310279707 A CN201310279707 A CN 201310279707A CN 103588169 A CN103588169 A CN 103588169A
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Prior art keywords
liquid fuel
devulcanizer
mentioned
gas
fuel
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CN201310279707.6A
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Chinese (zh)
Inventor
秋本淳
井深丈
樋渡学
渡边裕朗
市川德市
长谷川贵将
玉川晶子
西山拓雄
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Eneos Corp
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JX Nippon Oil and Energy Corp
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Priority claimed from JP2008127362A external-priority patent/JP5171384B2/en
Priority claimed from JP2008149550A external-priority patent/JP5226390B2/en
Priority claimed from JP2008159467A external-priority patent/JP4918068B2/en
Priority claimed from JP2008179516A external-priority patent/JP2010018467A/en
Priority claimed from JP2008179518A external-priority patent/JP5373327B2/en
Priority claimed from JP2008179392A external-priority patent/JP5171443B2/en
Application filed by JX Nippon Oil and Energy Corp filed Critical JX Nippon Oil and Energy Corp
Publication of CN103588169A publication Critical patent/CN103588169A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0675—Removal of sulfur
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
    • 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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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

The present invention provides a reforming system and a fuel cell system. The reforming system comprises a pump to send out liquid fuel, a desulfurizer arranged at a downstream side of the pump for removing a sulfuric content from the liquid fuel, a capillary tube arranged at a downstream side of the desulfurizer and passing the liquid fuel of which the sulfuric content is removed by the desulfurizer, a reformer arranged at a downstream side of the capillary tube and generating reforming gas containing hydrogen by using the liquid fuel of which the sulfuric content is removed by the desulfurizer.

Description

Reforming system and fuel cell system
Dividing an application of the patent application that the application's application number that to be applicant Shin Nihon Oil Co., Ltd propose on May 14th, 2009 is 200910137588.4, denomination of invention is " desulfurizer, fuel cell system and reforming system ".
Technical field
The present invention relates to reforming system and the fuel cell system with desulfurizer.
Background technology
In fuel cell system, utilize reformer to generate the reformed gas that contains hydrogen, utilize fuel cell stack (stack), with this reformed gas, generate electricity.In such fuel cell system, in the situation that be fed in reformer as the liquid fuels such as kerosene of reformer feed, in order to prevent the aging of reforming catalyst, need to be provided for removing the devulcanizer of desulfuration composition from liquid fuel.(for example,, with reference to 2004-No. 323285 communiques of TOHKEMY).
Summary of the invention
the 1st technical scheme of the present invention
But, in devulcanizer, in order to promote catalyzed reaction need to heat desulfurization catalyst, but because the temperature of heat tracing desulfurization catalyst rises, liquid fuel gasification, is not only difficult to carry out high efficiency desulfurization, and likely makes desulfurization catalyst aging.
Therefore, the 1st technical scheme of the present invention is to make in view of such situation, and object is to provide a kind of can prevent the desulfurizer of liquid fuel gasification and the fuel cell system with this desulfurizer.
In order to achieve the above object, the desulfurizer of the 1st technical scheme of the present invention is characterised in that, it comprises: devulcanizer, it is for accommodating desulfurization catalyst, this desulfurization catalyst for from will be supplied to the liquid fuel of reformer except desulfuration composition, this reformer is for generating the reformed gas that contains hydrogen; Heater block, it is for heating desulfurization catalyst; Liquid fuel imports parts, and it imports to liquid fuel in devulcanizer; Liquid fuel is derived parts, and it derives liquid fuel in devulcanizer; Temperature measurement unit, it is for measuring the temperature of the liquid fuel in devulcanizer; Pressure measurement unit, it is for measuring the pressure of the liquid fuel in devulcanizer; Function unit, heater block, liquid fuel are imported to parts for it and liquid fuel derivation parts are controlled, heater block, liquid fuel are imported to parts to function unit and liquid fuel derivation parts are controlled, making the temperature of being measured by temperature measurement unit is specified temperature, and the pressure of being measured by pressure measurement unit is that the saturation vapour pressure of the liquid fuel under specified temperature is above and be the withstand voltage following specified pressure of devulcanizer.
In this desulfurizer, by utilizing, function unit is controlled heater block, liquid fuel imports parts and liquid fuel is derived parts, thereby the temperature that makes to be measured by temperature measurement unit, is that the temperature of the liquid fuel in devulcanizer is for for example can promote the specified temperature of the catalyzed reaction of desulfurization catalyst.And, the pressure of being measured by pressure measurement unit, be that the pressure of the liquid fuel in devulcanizer is that the saturation vapour pressure of the liquid fuel under specified temperature is above and be the withstand voltage following specified pressure of devulcanizer.Thereby, even if make the temperature of the liquid fuel in devulcanizer increase, also can prevent liquid fuel gasification.In addition, so-called sulphur composition is the meaning that comprises sulphur and sulfide.And so-called devulcanizer withstand voltage refers to the maximum value of accommodating the interior pressure that the container of desulfurization catalyst can bear.
In the desulfurizer of the 1st technical scheme of the present invention, be preferably, function unit is controlled as follows: in the situation that make the pressure rise measured by pressure measurement unit, increase is imported the import volume of the liquid fuel of parts importing by liquid fuel, and reduce the derived quantity that is derived the liquid fuel of parts derivation by liquid fuel, in the situation that make the pressure decreased measured by pressure measurement unit, minimizing is imported the import volume of the liquid fuel of parts importing by liquid fuel, and increases the derived quantity that is derived the liquid fuel of parts derivation by liquid fuel.Adopting this structure, the pressure that can make to be measured by pressure measurement unit, is that the pressure of the liquid fuel in devulcanizer quickly and reliably rises or reduces.
And the fuel cell system of the 1st technical scheme of the present invention is characterised in that, it comprises: above-mentioned desulfurizer; With the liquid fuel that utilizes desulfurizer to remove sulphur composition, generate the reformer of the reformed gas that contains hydrogen; The fuel cell stack that the reformed gas that use utilizes reformer to generate generates electricity.
Adopt this fuel cell system, because there is above-mentioned desulfurizer, so even if make the temperature of the liquid fuel in devulcanizer increase, also can prevent liquid fuel gasification.
Adopt the 1st technical scheme of the present invention, can prevent the gasification of liquid fuel.
the 2nd technical scheme of the present invention
In fuel cell system, utilize reformer to generate the reformed gas that contains hydrogen, utilize fuel cell stack to generate electricity with this reformed gas.In such fuel cell system, in the situation that be fed in reformer as the liquid fuels such as kerosene of reformer feed, in order to prevent the aging of reforming catalyst, need to be provided for removing the devulcanizer of desulfuration composition from liquid fuel.(for example,, with reference to 2004-No. 323285 communiques of TOHKEMY).
But, in devulcanizer, in order to promote catalyzed reaction, need to heat desulfurization catalyst, but the desulfurization temperature (for example 200 ℃) that makes desulfurization catalyst rise to regulation from normal temperature needs considerable time.Therefore, exist once stop will the such problem of spended time to restarting.
Therefore, the 2nd technical scheme of the present invention is to make in view of such situation, and object is to provide a kind of and can seeks to shorten until the desulfurizer of the time of restarting and the fuel cell system with this desulfurizer.
In order to achieve the above object, the desulfurizer of the 2nd technical scheme of the present invention is characterised in that, it comprises: devulcanizer, it is for accommodating desulfurization catalyst, this desulfurization catalyst for from will be supplied to the liquid fuel of reformer except desulfuration composition, this reformer is for generating the reformed gas that contains hydrogen; Heater block, it is for heating desulfurization catalyst; Liquid fuel imports parts, and it imports to liquid fuel in devulcanizer; Liquid fuel is derived parts, and it derives liquid fuel in devulcanizer; Temperature measurement unit, it is for measuring the temperature of the liquid fuel in devulcanizer; Function unit, it derives parts for controlling heater block, liquid fuel importing parts and liquid fuel, function unit liquid fuel is imported parts and liquid fuel and derives parts at least one control, make in the situation that above-mentioned function unit input is had to halt signal, stop from feeding liquid fuel in devulcanizer, and heater block is controlled, made the temperature of being measured by measurement component be higher than normal temperature and compare the low specified temperature of temperature while conventionally turning round.
In this desulfurizer, in the situation that input has halt signal, by utilizing function unit to control liquid fuel, import at least one that parts and liquid fuel are derived parts, and stop from feeding liquid fuel in devulcanizer.Now, by utilizing function unit to control heater block, and by the temperature of being measured by temperature measurement unit, be that the temperature of the liquid fuel in devulcanizer is retained the specified temperature below and temperature during for running conventionally higher than normal temperature.Thus, the situation that makes temperature be reduced to normal temperature with desulfurizer is stopped is compared, and due to until the time of the desulfurization temperature of the temperature while being heated into common running, regulation is shortened, therefore can seek to shorten until the time of restarting.In addition, so-called sulphur composition is the meaning that comprises sulphur and sulfide.
In the desulfurizer of the 2nd technical scheme of the present invention, be preferably, also comprise by the temporary transient storage vessel storing of the liquid fuel of being derived parts derivation by liquid fuel, for measuring the storage capacity measurement component of the storage capacity of the liquid fuel that is stored in storage vessel, storage capacity measurement component, in the situation that storage capacity reaches regulation storage capacity, outputs to halt signal in function unit.Adopt this structure, by liquid fuel is temporarily stored in storage vessel, can make liquid fuel to the supply stabilization in reformer etc.Therefore and in the situation that the storage capacity in storage vessel reaches regulation storage capacity, storage capacity measurement component outputs to halt signal in function unit, can prevent such as the breakage by the caused storage vessel of storage capacity excess etc.
And the fuel cell system of the 2nd technical scheme of the present invention comprises: above-mentioned desulfurizer; The liquid fuel that use utilizes desulfurizer to remove sulphur composition generates the reformer of the reformed gas that contains hydrogen; The fuel cell stack that the reformed gas that use utilizes reformer to generate generates electricity.
Adopt this fuel cell system, there is above-mentioned desulfurizer, therefore can seek to shorten to the time of restarting.
Adopt the 2nd technical scheme of the present invention, can seek to shorten to the time of restarting.
the 3rd technical scheme of the present invention
In fuel cell system, utilize reformer to generate the reformed gas that contains hydrogen, utilize fuel cell stack to use this reformed gas to generate electricity.In such fuel cell system, in the situation that be fed in reformer as the liquid fuels such as kerosene of reformer feed, in order to prevent the aging of reforming catalyst, need to be provided for removing the devulcanizer of desulfuration composition from liquid fuel.(for example,, with reference to 2004-No. 323285 communiques of TOHKEMY).
But, in devulcanizer in, along with the reduction of the temperature of liquid fuel, pressure decreased.For example, when shutting down, when turning round conventionally, pressure ratio approximately reduces by 20% left and right.Now, liquid fuel likely gasifies, and makes desulfurization catalyst aging.And, when the pressure in devulcanizer becomes negative pressure, also may produce the breakage of devulcanizer, the medium such problem of inclusion of air devulcanizer while restarting to turn round.
Therefore, the 3rd technical scheme of the present invention is to make in view of such situation, and object is to provide a kind of fuel cell system of bringing dysgenic desulfurizer and have this desulfurizer to devulcanizer because of pressure decreased of preventing.
In order to achieve the above object, the desulfurizer of the 3rd technical scheme of the present invention is characterised in that, it comprises: devulcanizer, it is for accommodating desulfurization catalyst, this desulfurization catalyst for from will be supplied to the liquid fuel of reformer except desulfuration composition, this reformer is for generating the reformed gas that contains hydrogen; Liquid fuel imports parts, and it imports to liquid fuel in devulcanizer; Liquid fuel is derived parts, and it derives liquid fuel in devulcanizer; Temperature measurement unit, it is for measuring the temperature of the liquid fuel in devulcanizer; Pressure measurement unit, it is for measuring the pressure of the liquid fuel in devulcanizer; Function unit, it imports parts and liquid fuel derivation parts for controlling liquid fuel, liquid fuel is imported to parts to function unit and liquid fuel derivation parts are controlled, make in the situation that below the temperature of being measured by the temperature measurement unit specified temperature that to be temperature during than common running low, the pressure of being measured by pressure measurement unit is the specified pressure as malleation.
In this desulfurizer, for example, for example, in the situation that the temperature of being measured by temperature measurement unit, be that the temperature of the liquid fuel in devulcanizer is below the specified temperature (100 ℃) that temperature (200 ℃) during than common running is low, by utilizing function unit to control liquid fuel, import parts and liquid fuel derivation parts, making the pressure of being measured by pressure measurement unit is the specified pressure as malleation (more than negative pressure).Therefore, for example, when shutting down, even along with the reduction of the temperature of liquid fuel, pressure decreased, because the specified pressure as malleation is held, so also can prevent the such detrimentally affects to devulcanizer such as breakage such as liquid fuel gasification, devulcanizer that cause because of pressure decreased.In addition, so-called sulphur composition is the meaning that comprises sulphur and sulfide.
In the desulfurizer of the 3rd technical scheme of the present invention, preferably function unit is controlled as follows: in the situation that make the pressure rise measured by pressure measurement unit, increase is imported the import volume of the liquid fuel of parts importing by liquid fuel, and reduce the derived quantity that is derived the liquid fuel of parts derivation by liquid fuel, in the situation that make the pressure decreased measured by pressure measurement unit, minimizing is imported the import volume of the liquid fuel that parts import by liquid fuel, and increase by liquid fuel derive liquid fuel that parts derive derived quantity.Adopting this structure, the pressure that can quickly and reliably make to be measured by pressure measurement unit, is pressure rise or the reduction of the liquid fuel in devulcanizer.
And the fuel cell system of the 3rd technical scheme of the present invention, comprising: above-mentioned desulfurizer; The liquid fuel that use utilizes desulfurizer to remove sulphur composition generates the reformer of the reformed gas that contains hydrogen; The fuel cell stack that the reformed gas that use utilizes reformer to generate generates electricity.
Adopt this fuel cell system, there is above-mentioned desulfurizer, even if therefore pressure reduces along with the reduction of the temperature of liquid fuel, also can prevent detrimentally affect devulcanizer being caused because of pressure decreased.
Adopt the 3rd technical scheme of the present invention, can prevent detrimentally affect devulcanizer being caused because of pressure decreased.
the 4th technical scheme of the present invention
In fuel cell system, utilize reformer to generate the reformed gas that contains hydrogen, utilize fuel cell stack, use this reformed gas to generate electricity.In such fuel cell system, in the situation that be fed in reformer as the liquid fuels such as kerosene of reformer feed, in order to prevent the aging of reforming catalyst, need to be provided for removing the devulcanizer of desulfuration composition from liquid fuel.(for example,, with reference to 2004-No. 323285 communiques of TOHKEMY).
But, because the gases such as biogas and hydrogen are discharged from devulcanizer together with liquid fuel, therefore may occur to hinder to reformer liquid quantitative feeding fuel etc., the back segment of devulcanizer is brought to detrimentally affect.
Therefore, the 4th technical scheme of the present invention is to make in view of such situation, and object is to provide a kind of and can prevents the detrimentally affect of back segment and can from liquid fuel, remove reliably the desulfurizer of desulfuration composition and the fuel cell system with this desulfurizer.
In order to achieve the above object, the desulfurizer of the 4th technical scheme of the present invention is characterised in that, it comprises: devulcanizer, its for from will be supplied to the liquid fuel of reformer except desulfuration composition, this reformer is for generating the reformed gas that contains hydrogen; Gas-liquid separation container, it is for storing liquid fuel and the gas of discharging from devulcanizer; Liquid fuel vent line, it is for from gas-liquid separation container draining liquid fuel; Gas outlet pipe line, it is for from gas-liquid separation container Exhaust Gas; Open and close valve, it is located on gas outlet pipe line, for opening and closing the circulation of gas; Throttle part (throttle part of the pressure decreased in the devulcanizer when circulation that is suppressed at gas is opened), its downstream side at open and close valve is located on gas outlet pipe line, for hindering the circulation of gas.
In this desulfurizer, the gas being discharged from from devulcanizer together with liquid fuel is separated with liquid fuel gas-liquid separation container, via gas outlet pipe line, from gas-liquid separation container, is discharged from.The liquid fuel that therefore, can prevent from having sneaked into gas is fed into the back segment of desulfurizer.And, on gas outlet pipe line, in the downstream side that opens and closes the open and close valve of gas communication, be provided with the throttle part that hinders gas communication.Therefore,, even for gas is discharged and utilized open and close valve to open the circulation of gas from gas-liquid separation container via gas outlet pipe line, the reduction of the pressure in devulcanizer also can be suppressed by throttle part.Therefore, adopt this desulfurizer, can prevent the detrimentally affect of back segment and can from liquid fuel, remove reliably desulfuration composition.In addition, so-called sulphur composition is the meaning that comprises sulphur and sulfide.
In the desulfurizer of the 4th technical scheme of the present invention, be preferably, in the situation that open and close valve is closed the circulation of gas, when the amount of the gas in gas-liquid separation container has surpassed specified amount, open and close valve is opened the circulation of gas several times.Adopt this structure, the pressure decreased in the devulcanizer in the time of suppressing more reliably the circulation for gas is opened to gas from the discharge of gas-liquid separation container by open and close valve via gas outlet pipe line.
In the desulfurizer of the 4th technical scheme of the present invention, preferred gas vent line is connected with the burner that the reforming catalyst of reformer is heated.Adopt this structure, can effectively utilize the gas that is discharged from from devulcanizer as the fuel of burner together with liquid fuel.
And the fuel cell system of the 4th technical scheme of the present invention, comprising: above-mentioned desulfurizer; The liquid fuel that use utilizes desulfurizer to remove sulphur composition generates the reformer of the reformed gas that contains hydrogen; The fuel cell stack that the reformed gas that use utilizes reformer to generate generates electricity.
Adopt this fuel cell system, there is above-mentioned desulfurizer, therefore can prevent the detrimentally affect of the back segment of desulfurizer and can from liquid fuel, remove reliably desulfuration composition.
Adopt the 4th technical scheme of the present invention, can prevent the back segment detrimentally affect to desulfurizer, and can be reliably except desulfuration composition from liquid fuel.
the 5th technical scheme of the present invention
In fuel cell system, liquid fuel etc. is reformed and manufactured the reformed gas that comprises hydrogen, make the oxygen containing gas of this reformed gas and bag react and generate electricity.In the situation that use fuel that kerosene etc. comprises sulphur composition as the crude fuel of putting in fuel cell system, reforming catalyst is due to the sulphur composition in contact crude fuel, therefore sulfur poisoning occurs and makes the ageing of performance of reforming.Therefore,, as fuel cell system, sometimes before reforming reaction, from crude fuel, remove desulfuration composition.(for example,, with reference to 2004-No. 213941 communiques of TOHKEMY).
But, in the situation that the sulphur concentration being contained in crude fuel is higher, for fully, except desulfuration composition, consider to make the pressure in devulcanizer promote desulphurization reaction for the pressure higher than normal atmosphere.But, the in the situation that of being high pressure in making devulcanizer, the liquid fuel of high pressure can flow in the reformer of back segment from this devulcanizer.In this case, be difficult to control the flow of the liquid fuel of high pressure, reformation performance reduces, and as the performance of fuel cell system, reduces.And while being high pressure in making devulcanizer, the equipment such as the pipe arrangement of back segment, reaction vessel, pump produce the problem of weather resistance, these equipment need to adapt to high pressure phase, and cost improves.
Therefore, even if the object of the 5th technical scheme of the present invention is to provide in a kind of situation of under high pressure carrying out desulfurization, also can improve devulcanizer back segment equipment weather resistance, realize low-cost and prevent the fuel cell system that performance reduces.
The fuel cell system of the 5th technical scheme of the present invention is characterised in that, it comprises: devulcanizer, its under the pressure higher than normal atmosphere from the crude fuel of liquid except desulfuration composition and generate liquid fuel; Oil storage vessel, it is provided with and venting hole towards atmosphere opening, for storing the liquid fuel of discharging from devulcanizer; Send out pump, it sends liquid fuel in oil storage vessel; Reformer, it is configured in the downstream side of Send out pump, and liquid fuel is reformed and generated reformed gas; Fuel cell stack, it uses reformed gas to generate electricity.
In the fuel cell system of the 5th technical scheme of the present invention, the oil storage vessel of storage liquid fluid fuel is configured between the devulcanizer and reformer that under high pressure carries out desulphurization reaction, is provided with and venting hole towards atmosphere opening on this oil storage vessel.Therefore,, when the liquid fuel of the high pressure being desulfurized flows in oil storage vessel, be contained in gas in liquid fuel with liquid fuel separated and be discharged from oil storage vessel by venting hole in devulcanizer.Because the gas being contained in liquid fuel is discharged, therefore in the downstream side of oil storage vessel, can increase the reliability of the flow control of liquid fuel.Therefore, can control reliably the flow that flow into the liquid fuel in reformer, the reduction of the performance that prevents from reforming.And, because the liquid fuel of high pressure conditions does not flow into the downstream side of oil storage vessel, therefore do not need the equipment that adapts to high pressure phase, can improve the weather resistance of equipment of the back segment of oil storage vessel, can realize low cost.
In the fuel cell system of the 5th technical scheme of the present invention, preferably include with constant voltage crude fuel positive delivery to enter constant pressure pump in devulcanizer, be configured in the downstream side of devulcanizer and be configured in the kapillary of the upstream side of oil storage vessel.
In this case, crude fuel flows in devulcanizer with constant voltage, from the discharge of devulcanizer by throttling.Therefore, do not use the pump of high price, just can make pressure in devulcanizer higher than normal atmosphere, and can the flow of crude fuel (liquid fuel) be kept lowlyer.It is generally acknowledged also and can utilize the alternative kapillaries such as throttle orifice, needle type valve.But, there is the limit in the stream that extends throttle orifice part, therefore for the flow of the liquid fuel of the high pressure that reduces to be discharged from from devulcanizer, has to make the diameter of throttle orifice part minimum.At this, in devulcanizer, utilize desulfurization catalyst to carry out the desulfurization of liquid fuel, but desulfurization catalyst is included in the liquid fuel that utilizes devulcanizer to remove sulphur composition sometimes.Therefore,, in the situation that having utilized throttle orifice, needle type valve etc., the desulfurization catalyst flowing out from devulcanizer stops up the stream of throttle orifice part sometimes.With respect to this, in fuel cell system of the present invention, used as described above kapillary, therefore can, according to length capillaceous, increase to a certain extent internal diameter capillaceous.The situation of the obstruction that therefore, extremely difficult generation is caused by desulfurization catalyst.
In the fuel cell system of the 5th technical scheme of the present invention, preferably include: gas-liquid separation container, it is for by the liquid fuel of discharging from devulcanizer and gas delivery; Liquid fuel vent line, it is for from gas-liquid separation container draining liquid fuel; Gas outlet pipe line, it is for from gas-liquid separation container Exhaust Gas; Open and close valve, it is arranged on gas outlet pipe line, for opening and closing the circulation of gas; Throttle part, it is arranged on the downstream side of the open and close valve of gas outlet pipe line, for hindering gas communication; Under meter, it is arranged on liquid fuel vent line, and kapillary is arranged on the upstream side of the under meter in liquid fuel vent line, and downstream side and the liquid fuel vent line of the under meter on oil storage vessel liquid fuel within vent line are connected.
In this case, the gas being discharged from from devulcanizer together with liquid fuel is separated with liquid fuel at gas-liquid separation container, via gas outlet pipe line, from gas-liquid separation container, is discharged from.On gas outlet pipe line, in the downstream side of open and close valve that opens and closes the circulation of gas, be provided with the throttle part that hinders gas communication.Therefore,, even the circulation for gas is opened to gas via gas outlet pipe line from the discharge of gas-liquid separation container by open and close valve, the reduction of the pressure in devulcanizer also can be suppressed by throttle part.Therefore,, by the pressure in devulcanizer is remained on to high pressure, can from crude fuel, remove reliably desulfuration composition.On the other hand, liquid fuel flow in oil storage vessel via liquid fuel vent line.Therefore because liquid fuel within vent line is provided with under meter, can stably measure the flow of the liquid fuel after separated from the gas.
In the fuel cell system of the 5th technical scheme of the present invention, preferably include: water level sensor, it is for measuring low-water level and the high-water of the liquid fuel in oil storage vessel; Timing register, it is for measuring water level sensor from low-water level being detected to the time that high-water detected; Arithmetic facility, its Measuring Time based on timing register, calculates the flow of liquid fuel.
In this case, utilize timer measuring water level sensor from low-water level being detected to the time that high-water detected, the Measuring Time of arithmetic facility based on timing register calculated the flow of liquid fuel, therefore do not need to arrange in addition under meter.Thus, can seek more cost degradation.
In the fuel cell system of the 5th technical scheme of the present invention, preferably the bottom of oil storage vessel is as playing a role for accumulate the catalyst plate reservoir of the desulfurization catalyst sheet flowing into from devulcanizer together with liquid fuel, and the influx of the liquid fuel in oil storage vessel and spout are positioned at the top of catalyst plate reservoir.
In this case, the desulfurization catalyst flowing out can be stored in oil storage vessel together with liquid fuel from devulcanizer, make in its reformer that does not flow into back segment.And, the top that is positioned at catalyst plate reservoir due to influx and the spout of the liquid fuel in oil storage vessel, therefore, utilize inflow and the outflow of liquid fuel, the catalyzer that can suppress to be stored in catalyst plate reservoir flies upward, from storage tanks, flows out and flow in reformer.
In the fuel cell system of the 5th technical scheme of the present invention, preferably include: food tray, it is configured in the below of oil storage vessel; Upflow tube, one opening is disposed in oil storage vessel, and it is outer and downward, towards food tray, configure that another opening is configured in oil storage vessel; Leak sensor, it is configured in food tray.
In this case, even because certain is former thereby liquid fuel is riddled in oil storage vessel, liquid fuel also can flow through upflow tube and flow to food tray.And, can utilize the leak sensor being configured in food tray to detect liquid fuel and flow in food tray.
In the fuel cell system of the 5th technical scheme of the present invention, preferably there is the burner that reformer is heated, the fuel of the burning use using the eluting gas flowing out from venting hole as this burner.
In this case, can prevent that the eluting gas flowing out from venting hole from flowing to fuel cell system around.And, use eluting gas as the fuel of burner, therefore can contribute to energy-conservation.
Adopt the fuel cell system of the 5th technical scheme of the present invention, even if under high pressure carry out in the situation of desulfurization, also can improve the weather resistance of equipment of the back segment of devulcanizer, can realize low-cost and prevent that performance from reducing.
the 6th technical scheme of the present invention
In fuel cell system, using liquid fuel etc. as crude fuel, in reformer, this liquid fuel etc. is reformed and manufactured the reformed gas that comprises hydrogen, make the oxygen containing gas reaction of this reformed gas and bag and generate electricity.
But, in the situation that use fuel that kerosene etc. comprises sulphur composition as liquid fuel, reforming catalyst due to be present in liquid fuel sulphur composition contact, so can there is sulfur poisoning in reforming catalyst, the performances such as generation time shortening aging.Therefore,, in order to prevent the aging of reforming catalyst, fuel cell system generally has the devulcanizer (for example,, with reference to 2004-No. 213941 communiques of TOHKEMY) that removes desulfuration composition from liquid fuel.
But, in order to embody the performance of desulfurization catalyst, preferably making the temperature in devulcanizer is high temperature (for example, 200 ℃ of left and right).In addition, when making in this wise in devulcanizer as high temperature, can produce gas (biogas and hydrogen etc.), the flow of the liquid fuel (kerosene) of therefore supplying with easily reduces, or liquid fuel (kerosene) gasifies and generation knot carbon (coking) (carbon is separated out on the surface at desulfurization catalyst), the weather resistance of desulfurization catalyst easily reduces, therefore in order to suppress these, preferably the pressure in devulcanizer is high pressure (for example, 0.5MPa left and right).
But, make in the interior situation in High Temperature High Pressure of devulcanizer, it is large that the flow of liquid fuel becomes.Therefore, in the small-sized fuel cell system at needs for example, with utmost point low flow (, being that 10g/min is following during the fuel cell system of 1kW) transporting liquid fuel, the problem how existence must be lower by the flow control of liquid fuel.Now, expect utilizing low flow pump, but low flow pump price being very high, is not real options yet.
Therefore, the 6th technical scheme object of the present invention is to provide a kind of energy simple while realize fuel cell system and the reforming system with low flow transporting liquid fuel with low cost.
The fuel cell system of the 6th technical scheme of the present invention is characterised in that, it comprises: pump, and it is for delivery of liquid fuel; Devulcanizer, it is configured in the downstream side of pump, for removing desulfuration composition from liquid fuel; Kapillary, it is configured in the downstream side of devulcanizer, for the liquid fuel that utilizes devulcanizer to remove sulphur composition, passes through; Reformer, it is configured in downstream side capillaceous, uses the liquid fuel that utilizes devulcanizer to remove sulphur composition to generate the reformed gas that contains hydrogen; Fuel cell stack, the reformed gas that its use utilizes reformer to generate generates electricity.
In the fuel cell system of the 6th technical scheme of the present invention, at the downstream side of devulcanizer configuration kapillary.Therefore, by suitable selection internal diameter capillaceous and length, do not use the pump of high price, the size of the flow that just can make pressure in devulcanizer and liquid fuel for expecting.Its result, can simply and with low cost realize with low flow transporting liquid fuel.
But, also expect utilizing throttle orifice, needle type valve etc. to substitute kapillary.But, there is the limit in the stream that extends throttle orifice part, therefore, for the flow of the liquid fuel of the high pressure that reduces to be discharged from from devulcanizer, has to make the diameter of throttle orifice part minimum.At this, in devulcanizer, utilize desulfurization catalyst to carry out the desulfurization of liquid fuel, but desulfurization catalyst is contained in and utilize devulcanizer to remove in the liquid fuel of sulphur composition sometimes.Therefore,, in the situation that utilizing throttle orifice, needle type valve etc., the desulfurization catalyst sometimes flowing out from devulcanizer can stop up the stream of throttle orifice part.
But, in the fuel cell system of the 6th technical scheme of the present invention, use as described above kapillary, therefore according to length capillaceous, can increase to a certain extent internal diameter capillaceous.Therefore the obstruction that, extremely difficult generation is caused by desulfurization catalyst.
Preferred pump is constant pressure pump.Like this, the pressure in manageable devulcanizer.
Preferred internal diameter capillaceous is 0.lmm～0.7mm.When the not enough 0.lmm of internal diameter capillaceous, exist and easily occur to stop up tendency capillaceous by desulfurization catalyst.When internal diameter capillaceous surpasses 0.7mm, in order to be maintained high pressure in devulcanizer on one side with low flow transporting liquid fuel on one side, required total length capillaceous is elongated, has the tendency that is difficult to miniaturization.
Refin tubule is wound into spirrillum.Like this, even in the elongated situation of total length capillaceous, volume can be very not large yet.
On the other hand, the reforming system of the 6th technical scheme of the present invention is characterised in that, it comprises: pump, and it is for delivery of liquid fuel; Devulcanizer, it is configured in the downstream side of pump, for removing desulfuration composition from liquid fuel; Kapillary, it is configured in the downstream side of devulcanizer, for the liquid fuel that utilizes devulcanizer to remove sulphur composition, passes through; Reformer, it is configured in downstream side capillaceous, uses the liquid fuel that utilizes devulcanizer to remove sulphur composition to generate the reformed gas that contains hydrogen.
In the reforming system of the 6th technical scheme of the present invention, at the downstream side of devulcanizer configuration kapillary.Therefore, by suitable selection internal diameter capillaceous and length, do not use the pump of high price, the size of the flow that just can make pressure in devulcanizer and liquid fuel for expecting.Its result, can be easy and realize with low flow transporting liquid fuel with low cost.
But, also expect utilizing throttle orifice, needle type valve etc. to substitute kapillary.But, there is the limit in the stream that extends throttle orifice part, therefore, for the flow of the liquid fuel of the high pressure that reduces to discharge from devulcanizer, has to make the diameter of throttle orifice part minimum.At this, in devulcanizer, utilize desulfurization catalyst to carry out the desulfurization of liquid fuel, but desulfurization catalyst is contained in and utilize devulcanizer to remove in the liquid fuel of sulphur composition sometimes.Therefore,, in the situation that utilizing throttle orifice, needle type valve etc., the desulfurization catalyst sometimes flowing out from devulcanizer can stop up the stream of throttle orifice part.
But, in the fuel cell system of the 6th technical scheme of the present invention, use as described above kapillary, therefore according to length capillaceous, can increase to a certain extent internal diameter capillaceous.Therefore the obstruction that, extremely difficult generation is caused by desulfurization catalyst.
Preferred pump is constant pressure pump.Like this, the pressure in manageable devulcanizer.
Preferred internal diameter capillaceous is 0.lmm～0.7mm.When the not enough 0.lmm of internal diameter capillaceous, exist and easily occur to stop up tendency capillaceous by desulfurization catalyst.When internal diameter capillaceous surpasses 0.7mm, in order to be maintained high pressure in devulcanizer on one side with low flow transporting liquid fuel on one side, required total length capillaceous is elongated, has the tendency that is difficult to miniaturization.
Refin tubule is wound into spirrillum.Like this, even in the elongated situation of total length capillaceous, volume can be very not large yet.
Adopt the 6th technical scheme of the present invention, can provide a kind of easy and realize fuel cell system and the reforming system with low flow transporting liquid fuel with low cost.
Accompanying drawing explanation
Fig. 1 is the pie graph of an embodiment of the fuel cell system of the 1st embodiment.
Fig. 2 is the pie graph of the desulfurizer that has of the fuel cell system of Fig. 1.
Fig. 3 means the graphic representation of the relation between the temperature and pressure of the liquid fuel in the devulcanizer of desulfurizer of Fig. 2.
Fig. 4 means the schema of startup work of the desulfurizer of Fig. 2.
Fig. 5 is the pie graph of embodiment of the fuel cell system of the 2nd embodiment.
Fig. 6 is the pie graph of the desulfurizer that has of the fuel cell system of Fig. 5.
Fig. 7 means the running condition of desulfurizer of Fig. 6 and the figure of an example of the relation between design temperature.
Fig. 8 means the schema of work of the desulfurizer of Fig. 6.
Fig. 9 is the pie graph of an embodiment of the fuel cell system of the 3rd embodiment.
Figure 10 is the pie graph of the desulfurizer that has of the fuel cell system of Fig. 9.
Figure 11 means the table of the relation between the temperature and pressure when running of the desulfurizer of Figure 10 stops.
Figure 12 means the out-of-work schema of the desulfurizer of Figure 10.
Figure 13 is the pie graph of an embodiment of the fuel cell system of the 4th embodiment.
Figure 14 means the graphic representation of relation of pressure of floatswitch, magnetic valve and the devulcanizer of the fuel cell system of Figure 13.
Figure 15 is the figure that summary represents the fuel cell system of the 5th embodiment.
Figure 16 means the figure of the oil storage vessel that the fuel cell system of the 5th embodiment has.
Figure 17 means the figure of the oil storage vessel that the fuel cell system of the 5th embodiment has.
Figure 18 is the figure of the variation of the summary fuel cell system that represents the 5th embodiment.
Figure 19 means the figure of the variation of the oil storage vessel that the fuel cell system of the 5th embodiment has.
Figure 20 means in the variation of Figure 19, the figure of the control part that the fuel cell system of the 5th embodiment has.
Figure 21 means the figure of the variation of the oil storage vessel that the fuel cell system of the 5th embodiment has.
Figure 22 is the figure that summary represents the fuel cell system of the 6th embodiment.
Figure 23 is the figure of another example of the summary fuel cell system that represents the 6th embodiment.
Embodiment
the 1st embodiment
Below with reference to Fig. 1～Fig. 4, the fuel cell system 1 of the 1st embodiment is described in detail.
Fig. 1 is the pie graph of an embodiment of the fuel cell system of the 1st embodiment.As shown in Figure 1, fuel cell system 1 comprises: the reformer 2 that generates the reformed gas that contains hydrogen; From will be supplied to the liquid fuel reformer 2, remove the desulfurizer 3 of desulfuration composition; The fuel cell stack 4 that the reformed gas that use is generated by reformer 2 generates electricity.Fuel cell system 1, for example as home-use power supply, from easily obtaining and can independently storing this respect, is used kerosene as liquid fuel.
Reformer 2 comprises: liquid fuel is carried out steam reforming and generates the reformer 5 of reformed gas; The burner 6 that the reforming catalyst being housed in reformer 5 is heated.Burner 6 is used for promoting the reforming catalyst of steam reforming reaction by heating, will make catalyzed reaction effectively bring into play required heat supply in reforming catalyst.In reformer 5, the liquid fuel gasification importing from desulfurizer 3 and become unstripped gas, utilizes reforming catalyst to promote the steam reforming reaction between unstripped gas and water vapour (water), generates the reformed gas of rich hydrogen (hydrogen rich).
Fuel cell stack 4 is that a plurality of battery cells are piled up and the polymer electrolyte fuel cell storehouse of formation, uses the reformed gas obtaining in reformer 2 to generate electricity.Each battery cell there is anode, negative electrode and be configured in anode and negative electrode between the electrolytical macroion exchange membrane of conduct.In each battery cell, reformed gas is directed to anode and air is directed to negative electrode, carries out electrochemistry electric power generation reaction.
Fig. 2 is the pie graph of the desulfurizer that has of the fuel cell system of Fig. 1.As shown in Figure 2, desulfurizer 3 has the devulcanizer 7 of accommodating desulfurization catalyst 7a, this desulfurization catalyst 7a for from will be supplied to the liquid fuel of reformer 5 except desulfuration composition.Desulfurization catalyst 7a is heated to specified temperature by well heater (heater block) 8.Upstream side at devulcanizer 7 is provided with the inlet valve (liquid fuel importing parts) 9 regulating to the import volume of the interior importing liquid fuel of devulcanizer 7.And, at the upstream side of inlet valve 9, be provided with the pump (liquid fuel importing parts) 11 liquid fuel being pressed and delivered in devulcanizer 7.On the other hand, in the downstream side of devulcanizer 7, be provided with the outlet valve (liquid fuel derivation parts) 12 regulating from the derived quantity of the liquid fuel in devulcanizer 7.
And, on devulcanizer 7, be provided with the thermometer (temperature measurement unit) 13 of the temperature of measuring the liquid fuel in devulcanizer 7.And, between devulcanizer 7 and inlet valve 9, be also provided with the pressure warning unit (pressure measurement unit) 14 of the pressure of measuring the liquid fuel in devulcanizer 7.The temperature of control part (function unit) 15 based on being measured by thermometer 13 and the pressure of being measured by pressure warning unit 14, control well heater 8, inlet valve 9, pump 11 and outlet valve 12.
As shown in Figure 1, desulfurizer 3 is connected with the one end of liquid fuel flow line 16 for being removed the liquid fuel circulation of sulphur composition, and the other end of liquid fuel flow line 16 is connected with the sidewall that is configured in the storage vessel 19 of desulfurizer 3 tops.The diapire of storage vessel 19 is connected with liquid fuel flow line 23, liquid fuel flow line 25, on this liquid fuel flow line 23, be provided with for by be stored in storage vessel 19 below liquid fuel import to the pump 22 of reformer 5, on this liquid fuel flow line 25, be provided with for this liquid fuel being imported to the pump 24 of burner 6.In addition, burner 6 is connected with being provided with for air being imported to the circulation of air pipeline 27 of the pump 26 of burner 6.Like this, by liquid fuel is temporarily stored in storage vessel 19, can make the supply of liquid fuel of 22 pairs of reformers 5 of pump and the supply stabilization of the liquid fuel of 24 pairs of burners 6 of pump.
In the fuel cell system 1 forming as described above, first liquid fuel is directed in the devulcanizer 7 of desulfurizer 3, under the state of high temperature, high pressure, utilizes desulfurization catalyst 7a except desulfuration composition.The liquid fuel being exported from devulcanizer 7 is stored into storage vessel 19 via liquid fuel flow line 16.The liquid fuel being stored in storage vessel 19 is directed in reformer 5 via liquid fuel flow line 23.Now, liquid fuel is directed in burner 6 via liquid fuel flow line 25, and air is directed in burner 6 via circulation of air pipeline 27.Thus, in reformer 5,6 heating of burner that reforming catalyst is burnt, are used liquid fuel and generate reformed gas.The reformed gas generating in reformer 5 is directed in fuel cell stack 4, in fuel cell stack 4, uses reformed gas to generate electricity.
The work of desulfurizer 3 then, is described.Fig. 3 means the graphic representation of the relation between the temperature and pressure of the liquid fuel in the devulcanizer of desulfurizer of Fig. 2, and Fig. 4 means the schema of startup work of the desulfurizer of Fig. 2.
As shown in Figure 3, the target value of the pressure of liquid fuel during each temperature of the liquid fuel of control part 15 in devulcanizer 7, in devulcanizer 7 is stored as data sheet.The saturation vapour pressure of the liquid fuel when target value of this pressure is set to each temperature is above and for below devulcanizer 7 withstand voltage.That is to say, according to the temperature of the liquid fuel in devulcanizer 7, as long as the pressure of the liquid fuel in devulcanizer 7 is maintained to target value, just can prevent the gasification of liquid fuel.
As shown in Figure 4, when the startup work of desulfurizer 3 starts, 15 pairs of temperature of being measured by thermometer 13 of control part, be whether the temperature of the liquid fuel in devulcanizer 7 judges (step S11) than A is high.Its result be the temperature of the liquid fuel in devulcanizer 7 than in the low situation of A, in order to heat the desulfurization catalyst 7a in devulcanizer 7, control part 15 makes well heater 8 work (step S12), the judgement that turns back to step S11 is processed.
The result that the judgement of step S11 is processed be the temperature of the liquid fuel in devulcanizer 7 than in the high situation of A, 15 pairs of pressure of being measured by pressure warning unit 14 of control part, be whether the pressure of the liquid fuel in devulcanizer 7 judges (step S13) than X is high.Its result is in the situation that the pressure ratio X of the liquid fuel in devulcanizer 7 is low, for liquid fuel being imported in devulcanizer 7, control part 15 makes pump 11 work and opens inlet valve 9(step S14), also make well heater 8 stop (step S15), the judgement that turns back to step S13 is processed.
The judgement result of step S13 is in the situation that the pressure ratio X of the liquid fuel in devulcanizer 7 is high, and control part 15 stops pump 11 and closes inlet valve 9(step S16).Then, 15 pairs of temperature of being measured by thermometer 13 of control part, be whether the temperature of the liquid fuel in devulcanizer 7 judges (step S17) than B (>A) height.Its result be the temperature of the liquid fuel in devulcanizer 7 than in the low situation of B, in order to heat the desulfurization catalyst 7a in devulcanizer 7, control part 15 makes well heater 8 work (step S18), the judgement that turns back to step S17 is processed.
The judgement result of step S17 be the temperature of the liquid fuel in devulcanizer 7 than in the high situation of B, 15 pairs of pressure of being measured by pressure warning unit 14 of control part, be whether the pressure of the liquid fuel in devulcanizer 7 judges (step S19) than Y (>X) height.Its result is that liquid fuel pressure in devulcanizer 7 is than in the low situation of Y, for liquid fuel being imported in devulcanizer 7, control part 15 makes pump 11 work and opens inlet valve 9(step S20), also make well heater 8 stop (step S21), the judgement that turns back to step S19 is processed.
The judgement result of step S19 is in the situation that the pressure ratio Y of the liquid fuel in devulcanizer 7 is high, and control part 15 stops pump 11 and closes inlet valve 9(step S22).Then, 15 pairs of temperature of being measured by thermometer 13 of control part, be whether the temperature of the liquid fuel in devulcanizer 7 judges (step S23) than C (>B) height.Its result be the temperature of the liquid fuel in devulcanizer 7 than in the low situation of C, in order to heat the desulfurization catalyst 7a in devulcanizer 7, control part 15 makes well heater 8 work (step S24), the judgement that turns back to step S23 is processed.
The judgement result of step S23 be the temperature of the liquid fuel in devulcanizer 7 than in the high situation of C, 15 pairs of pressure of being measured by pressure warning unit 14 of control part, be whether liquid fuel pressure in devulcanizer 7 judges (step S25) than Z (>Y) height.Its result is in the situation that the pressure ratio Z of the liquid fuel in devulcanizer 7 is low, for liquid fuel being imported in devulcanizer 7, control part 15 makes pump 11 work and opens inlet valve 9(step S26), also make well heater 8 stop (step S27), the judgement that turns back to step S25 is processed.
The judgement result of step S25 is in the situation that the pressure ratio Z of the liquid fuel in devulcanizer 7 is high, and control part 15 stops pump 11 and closes inlet valve 9(step S28).Then, 15 pairs of temperature of being measured by thermometer 13 of control part, be whether the temperature of the liquid fuel in devulcanizer 7 judges (step S29) than D (>C) height.Its result be the temperature of the liquid fuel in devulcanizer 7 than in the low situation of D, in order to heat the desulfurization catalyst 7a in devulcanizer 7, control part 15 makes well heater 8 work (step S30), the judgement that turns back to step S29 is processed.
The judgement result of step S29 is that the temperature of the liquid fuel in devulcanizer 7 is than in the high situation of D, at this temperature, carry out desulfurization, for by the liquid fuel supply that has been removed sulphur composition in reformer 2, pump 11 is worked and open inlet valve 9 and outlet valve 12, the startup end-of-job of desulfurizer 3.
As above explanation is such, in the desulfurizer 3 of fuel cell system 1,15 pairs of well heaters 8 of control part, inlet valve 9, pump 11 and outlet valve 12 are controlled, the temperature that makes to be measured by thermometer 13, being that the temperature of the liquid fuel in devulcanizer 7 is specified temperature, the pressure of being measured, is that the pressure of the liquid fuel in devulcanizer 7 is that the saturation vapour pressure of the liquid fuel under specified temperature is above and be the withstand voltage following specified pressure (being target value) of devulcanizer by pressure warning unit 14.This not only when the startup work of desulfurizer 3, when the steady operation of desulfurizer 3 and while quitting work too.Therefore, even if make the temperature of the liquid fuel in devulcanizer 7 increase, also can prevent liquid fuel gasification, its result, can realize high efficiency desulfurization and suppress the aging of desulfurization catalyst 7a.
In the situation that make the pressure rise measured by pressure warning unit 14, control part 15 is worked pump 11 and is opened inlet valve 9 and the import volume of liquid fuel is increased, and closes outlet valve 12 and the derived quantity of liquid fuel is reduced.On the other hand, in the situation that make the pressure decreased measured by pressure warning unit 14, control part 15 stops pump 11 and closes inlet valve 9 and the import volume of liquid fuel is reduced, and opens outlet valve 12 derived quantity of liquid fuel is increased.The pressure that thus, can quickly and reliably make to be measured by pressure warning unit 14, be pressure rise or the reduction of the liquid fuel in devulcanizer 7.And so-called " close inlet valve 9(or outlet valve 12) " not only refer to and close completely and situation that flow is 0, also comprise and not closing completely and situation that flow reduces.
The 1st technical scheme of the present invention is not limited to above-mentioned embodiment.
For example, fuel cell stack 4 is not limited to polymer electrolyte fuel cell storehouse, can be also Solid Oxide Fuel Cell storehouse etc.
And reformer 5 is not limited to carry out the reformer of steam reforming, it can be also the reformer that carries out partial oxidation reformation, self thermal reforming.The reforming method of reformer 5 is based on outside kerosene, also according to gasoline, petroleum naphtha, light oil, methyl alcohol, ethanol, DME(dme), utilize the reforming method of characteristic of the liquid fuels such as biofuel of biological substance.
the 2nd embodiment
Below with reference to Fig. 5～Fig. 8, the fuel cell system 1 of the 2nd embodiment is described in detail.
Fig. 5 is the pie graph of an embodiment of the fuel cell system 1 of the 2nd embodiment.As shown in Figure 5, fuel cell system 1 comprises: the reformer 2 that generates the reformed gas that contains hydrogen; From will be supplied to the liquid fuel reformer 2, remove the desulfurizer 3 of desulfuration composition; The fuel cell stack 4 that the reformed gas that use is generated by reformer 2 generates electricity.Fuel cell system 1, for example as home-use power supply, from easily obtaining and can independently storing this respect, is used kerosene as liquid fuel.
Reformer 2 has to liquid fuel is carried out steam reforming and generates the reformer 5 of reformed gas and the burner 6 that the reforming catalyst being housed in reformer 5 is heated.Burner 6 is used for promoting the reforming catalyst of steam reforming reaction by heating, will make catalyzed reaction effectively bring into play required heat supply in reforming catalyst.In reformer 5, the liquid fuel gasification importing from desulfurizer 3 and become unstripped gas, utilizes reforming catalyst to promote the steam reforming reaction between unstripped gas and water vapour (water), generates the reformed gas of rich hydrogen.
Fuel cell stack 4 is that a plurality of battery cells are piled up and the polymer electrolyte fuel cell storehouse of formation, uses the reformed gas obtaining at reformer 2 to generate electricity.Each battery cell there is anode, negative electrode and be configured in anode and negative electrode between the electrolytical macroion exchange membrane of conduct.In each battery cell, reformed gas is directed to anode and air is directed to negative electrode, carries out electrochemical electric power generation reaction.
Fig. 6 is the pie graph of the desulfurizer that has of the fuel cell system of Fig. 5.As shown in Figure 6, desulfurizer 3 has the devulcanizer 7 of accommodating desulfurization catalyst 7a, this desulfurization catalyst 7a for from will be supplied to the liquid fuel of reformer 5 except desulfuration composition.Desulfurization catalyst 7a is heated to specified temperature by well heater (heater block) 8.Upstream side at devulcanizer 7 is provided with the inlet valve (liquid fuel importing parts) 9 regulating to the import volume of the interior importing liquid fuel of devulcanizer 7.And, at the upstream side of inlet valve 9, be provided with the pump (liquid fuel importing parts) 11 liquid fuel being pressed and delivered in devulcanizer 7.On the other hand, in the downstream side of devulcanizer 7, be provided with the outlet valve (liquid fuel derivation parts) 12 regulating from the derived quantity of the liquid fuel in devulcanizer 7.
And, on devulcanizer 7, be provided with the thermometer (temperature measurement unit) 13 of the temperature of measuring the liquid fuel in devulcanizer 7.And, between devulcanizer 7 and inlet valve 9, be provided with the pressure warning unit (pressure measurement unit) 14 of the pressure of measuring the liquid fuel in devulcanizer 7.When the signal of regulation is output, control part (function unit) 15 is controlled well heater 8, inlet valve 9, pump 11 and outlet valve 12 based on this signal.In addition, so-called specified signal is initiating signal, stop signal, halt signal, restarts CRANK PULSES.
As shown in Figure 5, desulfurizer 3 is connected with the one end of liquid fuel flow line 16 for being removed the liquid fuel circulation of sulphur composition, and the other end of liquid fuel flow line 16 is connected with the sidewall that is configured in the storage vessel 19 of desulfurizer 3 tops.In storage vessel 19, be provided with the liquid level meter (leveller) (storage capacity measurement component) 20 of measuring storage capacity.When the storage capacity of liquid level meter 20 in storage vessel 19 reaches the 1st storage capacity, to control part 15 output halt signals, when the storage capacity in storage vessel 19 reduces to than the 2nd storage capacity of the 1st storage capacity low level, to control part 15 outputs, restart CRANK PULSES.
And, the diapire of storage vessel 19 is connected with liquid fuel flow line 23, liquid fuel flow line 25, this liquid fuel flow line 23 is provided with for the liquid fuel that is stored in the below in storage vessel 19 being imported to the pump 22 of reformer 5, and this liquid fuel flow line 25 is provided with for this liquid fuel being imported to the pump 24 of burner 6.In addition, burner 6 is connected with being provided with for air being imported to the circulation of air pipeline 27 of the pump 26 of burner 6.Like this, by liquid fuel is temporarily stored in storage vessel 19, can make the supply of liquid fuel of 22 pairs of reformers 5 of pump and the supply stabilization of the liquid fuel of 24 pairs of burners 6 of pump.
In the fuel cell system 1 forming as described above, first liquid fuel is directed in the devulcanizer 7 of desulfurizer 3, under the state of high temperature, high pressure, utilizes desulfurization catalyst 7a except desulfuration composition.The liquid fuel being exported from devulcanizer 7 is stored into storage vessel 19 via liquid fuel flow line 16.The liquid fuel being stored in storage vessel 19 is directed in reformer 5 via liquid fuel flow line 23.Now, liquid fuel is directed in burner 6 via liquid fuel flow line 25, and air is directed in burner 6 via circulation of air pipeline 27.Thus, in reformer 5,6 heating of burner that reforming catalyst is burnt, are used liquid fuel and generate reformed gas.The reformed gas generating in reformer 5 is directed in fuel cell stack 4, in fuel cell stack 4, uses reformed gas to generate electricity.
The work of desulfurizer 3 then, is described.Fig. 7 means the running condition of desulfurizer of Fig. 6 and the figure of an example of the relation between design temperature, and Fig. 8 means the schema of work of the desulfurizer of Fig. 6.
As shown in Figure 7, the target value of the temperature of control part 15 in the devulcanizer of each running condition 7 is stored as data sheet.The target value of temperature: be for example 190 ℃～210 ℃ when conventionally turning round and (can promote the regulation desulfurization temperature of the catalyzed reaction of desulfurization catalyst 7a: temperature A), be 180 ℃～190 ℃ (temperature B) during time-out.Temperature B(specified temperature during time-out) be set to such an extent that the temperature A high and during than running conventionally of the temperature (5 ℃～35 ℃) when stopping is low.
As shown in Figure 8, when the common running of desulfurizer 3 startups, whether 15 pairs of control parts have inputted halt signal from liquid level meter 20 judges (step S11).Its result is to have inputted in the situation of halt signal, and in order to stop to the interior importing liquid fuel of devulcanizer 7, control part 15 stops pump 11 and closes inlet valve 9 and outlet valve 12(step S12).Then, control part 15 control heaters 8, make the temperature of the liquid fuel in devulcanizer 7 become temperature B(step S13).
After the processing of step S13, whether 15 pairs of control parts have been inputted and have been restarted CRANK PULSES and judge (step S14) from liquid level meter 20.Its result is to have inputted in the situation that restarts CRANK PULSES, and control part 15 control heaters 8 make the temperature of the liquid fuel in devulcanizer 7 become temperature A(step S15).Then, with temperature A, carry out desulfurization, for the liquid fuel that has been removed sulphur composition is re-supplied in reformer 2, makes pump 11 work and open inlet valve 9 and outlet valve 12(step S16), the judgement that turns back to step S11 is processed.On the other hand, in step S17, in the situation that input does not have the CRANK PULSES of restarting, this processing is until input has the CRANK PULSES of restarting repeatedly.
On the other hand, the judgement result of step S11 is not for inputting and have in the situation of halt signal, and whether 15 pairs of control parts have inputted stop signal judges (step S17).Its result has in the situation of stop signal for inputting, and control part 15 stops pump 11 and closes inlet valve 9 and outlet valve 12(step S18), also make well heater 8 stop (step S19), the running of desulfurizer 3 finishes.On the other hand, in the situation that input does not have stop signal, the judgement that turns back to step S11 is processed.And, by pressing for making for example button that the work of desulfurizer 3 stops and stop signal being input to control part 15.
As above explanation is such, in the desulfurizer 3 of fuel cell system 1, in the situation that liquid level meter 20 has been inputted halt signal, 15 pairs of inlet valves 9 of control part, pump 11 and outlet valve 12 are controlled, and make to stop from devulcanizer 7 interior to storage vessel 19 feeding liquid fuel.Now, control part 15 control heaters 8, the temperature that makes to be measured by thermometer 13, are that the temperature of the liquid fuel in devulcanizer 7 is maintained at the low specified temperature B(target value of temperature A higher than normal temperature and during than running conventionally).Thus, the situation that makes temperature be reduced to normal temperature with desulfurizer 3 is stopped is compared, and the time of the temperature A while being heated to common running, regulation desulfurization temperature is shortened, and therefore can seek to shorten until the time of restarting.
And as shown in Figure 7, the temperature A low temperature of the temperature B when making to suspend when than common running, can seek to reduce energy expenditure.And, by not making temperature B be reduced to normal temperature, can prevent that desulfurization catalyst 7a's that the temperature difference when with common running causes is aging when suspending.
And, there is the storage vessel 19 of temporary transient storage liquid fluid fuel, in the situation that the storage capacity of storage vessel 19 reaches the 1st storage capacity, liquid level meter 20 is to control part 15 output halt signals.On the other hand, the storage capacity of storage vessel 19 is reduced to than in the situation of the 2nd storage capacity of the 1st storage capacity low level, and liquid level meter 20 restarts CRANK PULSES to control part 15 outputs.Thus, can prevent the breakage etc. of the storage vessel 19 that causes such as storage capacity excess.And in the situation that reduce to the 2nd storage capacity than the 1st storage capacity low level, output restarts CRANK PULSES, the work of desulfurizer 3 restarts, and therefore can seek the efficient activity of operation.
The 2nd technical scheme of the present invention is not limited to above-mentioned embodiment.
For example, in the situation that input has halt signal, also can not close inlet valve 9 and outlet valve 12 these two, and only close inlet valve 9.
And, halt signal and restart CRANK PULSES also can be from liquid level meter 20 inputs, for example by giving as security knob down, input.
And fuel cell stack 4 is not limited to polymer electrolyte fuel cell storehouse, it can be also Solid Oxide Fuel Cell storehouse etc.
And reformer 5 is not limited to carry out the reformer of steam reforming, it can be also the reformer that carries out partial oxidation reformation, self thermal reforming.The reforming method of reformer 5 is based on outside kerosene, also according to gasoline, petroleum naphtha, light oil, methyl alcohol, ethanol, DME(dme), utilize the reforming method of characteristic of the liquid fuels such as biofuel of biological substance.
the 3rd embodiment
Below with reference to Fig. 9～Figure 12, the fuel cell system 1 of the 3rd embodiment is described in detail.
Fig. 9 is the pie graph of an embodiment of the fuel cell system of the 3rd embodiment.As shown in Figure 9, fuel cell system 1 comprises: the reformer 2 that generates the reformed gas that contains hydrogen; From will be supplied to the liquid fuel reformer 2, remove the desulfurizer 3 of desulfuration composition; The fuel cell stack 4 that the reformed gas that use is generated by reformer 2 generates electricity.Fuel cell system 1, for example as home-use power supply, from easily obtaining and can independently storing this respect, is used kerosene as liquid fuel.
Reformer 2 has to liquid fuel is carried out steam reforming and generates the reformer 5 of reformed gas and the burner 6 that the reforming catalyst being housed in reformer 5 is heated.Burner 6 is used for promoting the reforming catalyst of steam reforming reaction by heating, will make catalyzed reaction effectively bring into play required heat supply in reforming catalyst.In reformer 5, the liquid fuel gasification importing from desulfurizer 3 and become unstripped gas, utilizes reforming catalyst to promote the steam reforming reaction between unstripped gas and water vapour (water), generates the reformed gas of rich hydrogen.
Fuel cell stack 4 is that a plurality of battery cells are piled up and the polymer electrolyte fuel cell storehouse of formation, uses the reformed gas obtaining at reformer 2 to generate electricity.Each battery cell there is anode, negative electrode and be configured in anode and negative electrode between the electrolytical macroion exchange membrane of conduct.In each battery cell, reformed gas is directed to anode and air is directed to negative electrode, carries out electrochemical electric power generation reaction.
Figure 10 is the pie graph of the desulfurizer that has of the fuel cell system of Fig. 9.As shown in figure 10, desulfurizer 3 has the devulcanizer 7 of accommodating desulfurization catalyst 7a, this desulfurization catalyst 7a for from will be supplied to the liquid fuel of reformer 5 except desulfuration composition.Desulfurization catalyst 7a is heated to specified temperature by well heater (heater block) 8.Upstream side at devulcanizer 7 is provided with the inlet valve (liquid fuel importing parts) 9 regulating to the import volume of the interior importing liquid fuel of devulcanizer 7.And, at the upstream side of inlet valve 9, be provided with the pump (liquid fuel importing parts) 11 liquid fuel being pressed and delivered in devulcanizer 7.On the other hand, in the downstream side of devulcanizer 7, be provided with the outlet valve (liquid fuel derivation parts) 12 regulating from the derived quantity of the liquid fuel in devulcanizer 7.
On devulcanizer 7, be provided with the thermometer (temperature measurement unit) 13 of the temperature of measuring the liquid fuel in devulcanizer 7.And, between devulcanizer 7 and inlet valve 9, be provided with the pressure warning unit (pressure measurement unit) 14 of the pressure of measuring the liquid fuel in devulcanizer 7.The temperature of control part (function unit) 15 based on being measured by thermometer 13 and the pressure of being measured by pressure warning unit 14, control well heater 8, inlet valve 9, pump 11 and outlet valve 12.
As shown in Figure 9, desulfurizer 3 is connected with the one end of liquid fuel flow line 16 for being removed the liquid fuel circulation of sulphur composition, and the other end of liquid fuel flow line 16 is connected with the sidewall that is configured in the storage vessel 19 of desulfurizer 3 tops.The diapire of storage vessel 19 is connected with liquid fuel flow line 23, liquid fuel flow line 25, this liquid fuel flow line 23 is provided with for the liquid fuel that is stored in the below in storage vessel 19 being imported to the pump 22 of reformer 5, and this liquid fuel flow line 25 is provided with for this liquid fuel being imported to the pump 24 of burner 6.In addition, burner 6 is connected with being provided with for air being imported to the circulation of air pipeline 27 of the pump 26 of burner 6.Like this, by liquid fuel is temporarily stored in storage vessel 19, can make the supply of liquid fuel of 22 pairs of reformers 5 of pump and the supply stabilization of the liquid fuel of 24 pairs of burners 6 of pump.
In the fuel cell system 1 forming as described above, first liquid fuel is directed in the devulcanizer 7 of desulfurizer 3, under the state of high temperature, high pressure, utilizes desulfurization catalyst 7a except desulfuration composition.The liquid fuel being exported from devulcanizer 7 is stored into storage vessel 19 via liquid fuel flow line 16.The liquid fuel being stored in storage vessel 19 is directed in reformer 5 via liquid fuel flow line 23.Now, liquid fuel is directed in burner 6 via liquid fuel flow line 25, and air is directed in burner 6 via circulation of air pipeline 27.Thus, in reformer 5,6 heating of burner that reforming catalyst is burnt, are used liquid fuel and generate reformed gas.The reformed gas generating in reformer 5 is directed in fuel cell stack 4, in fuel cell stack 4, uses reformed gas to generate electricity.
The work of desulfurizer 3 then, is described.The chart of the relation between temperature and pressure when Figure 11 means the shutting down of desulfurizer of Figure 10, Figure 12 means the schema of work of the desulfurizer of Figure 10.
As shown in figure 11, the pressure low limit value (target value) in the devulcanizer 7 of each temperature range of control part 15 when stopping is stored as data sheet.The lower value of pressure: be for example 200kPa in when more than 150 ℃, be 100kPa in the time of 100 ℃～150 ℃.And, in time below 100 ℃, be for example 5kPa.Low 100 ℃ (specified temperature) following pressure of temperature during than common running is set to the specified pressure as malleation (more than negative pressure).
As shown in figure 12, the quitting work while starting of desulfurizer 3, in order to stop that liquid fuel is imported in devulcanizer 7, control part 15 stops pump 11 and closes inlet valve 9 and outlet valve 12(step S11), also make well heater 8 stop (step S12).
After the processing of step S12,15 pairs of control parts by the measured pressure of pressure warning unit 14, be the pressure specific pressure A(5kPa for example whether of the liquid fuel in devulcanizer 7) height judges (step S13).Its result is in the situation that the pressure ratio pressure A of the liquid fuel in devulcanizer 7 is high, and the judgement that turns back to step S13 is processed.On the other hand, in the situation that the pressure ratio pressure A of the liquid fuel in devulcanizer 7 is low, for liquid fuel being imported in devulcanizer 7, control part 15 is worked pump 11 and is opened inlet valve 9(step S14).
After the processing of step S14,15 pairs of pressure of being measured by pressure warning unit 14 of control part, being the pressure specific pressure B(40kPa for example whether of the liquid fuel in devulcanizer 7) height judges (step S15).Its result is in the situation that the pressure ratio pressure B of the liquid fuel in devulcanizer 7 is high, and in order to stop that liquid fuel is imported in devulcanizer 7, control part 15 stops pump 11 and closes inlet valve 9(step S16), the judgement that turns back to step S13 is processed.On the other hand, in the situation that the liquid fuel pressure specific pressure B in devulcanizer 7 is high, the judgement that turns back to step S15 is processed.
As above explanation is such, in the desulfurizer 3 of fuel cell system 1, in the situation that the temperature of being measured by thermometer 13, be that the temperature of the liquid fuel in devulcanizer 7 is below the specified temperature that temperature during than common running is low, 15 pairs of inlet valves 9 of control part, pump 11 and outlet valve 12 are controlled, and the pressure that makes to be measured by pressure warning unit 14, are that the pressure of the liquid fuel in devulcanizer 7 is the specified pressure as malleation.Therefore, for example, when shutting down, even if pressure reduces along with the reduction of the temperature of liquid fuel, because the specified pressure as malleation is held, therefore can prevent the gasification such as liquid fuel being caused by pressure decreased, such detrimentally affects to devulcanizer 7 such as breakage of devulcanizer 7.
In the situation that make the pressure rise measured by pressure warning unit 14, control part 15 is worked pump 11 and is opened inlet valve 9 and the import volume of liquid fuel is increased, and closes outlet valve 12 and the derived quantity of liquid fuel is reduced.On the other hand, in the situation that make the pressure decreased measured by pressure warning unit 14, control part 15 stops pump 11 and closes inlet valve 9 and the import volume of liquid fuel is reduced, and opens outlet valve 12 and the derived quantity of liquid fuel is increased.The pressure that thus, can quickly and reliably make to be measured by pressure warning unit 14, be pressure rise or the reduction of the liquid fuel in devulcanizer 7.And so-called " close inlet valve 9(or outlet valve 12) " not only refer to and close completely and situation that flow is 0, also comprise and not closing completely and situation that flow reduces.
The 3rd technical scheme of the present invention is not limited to above-mentioned embodiment.
For example, fuel cell stack 4 is not limited to polymer electrolyte fuel cell storehouse, can be also Solid Oxide Fuel Cell storehouse etc.
And reformer 5 is not limited to the reformer of steam reforming, can be also that partial oxidation is reformed, the reformer of self thermal reforming.The reforming method of reformer 5 is based on outside kerosene, also according to gasoline, petroleum naphtha, light oil, methyl alcohol, ethanol, DME(dme), utilize the reforming method of characteristic of the liquid fuels such as biofuel of biological substance.
the 4th embodiment
Below with reference to Figure 13 and Figure 14, the fuel cell system 1 of the 4th embodiment is described in detail.
Figure 13 is the pie graph of embodiment of the fuel cell system of the 4th embodiment.As shown in figure 13, fuel cell system 1 comprises: the reformer 2 that generates the reformed gas that contains hydrogen; From will be supplied to the liquid fuel reformer 2, remove the desulfurizer 3 of desulfuration composition; The fuel cell stack 4 that the reformed gas that use is generated by reformer 2 generates electricity.Fuel cell system 1, for example as home-use power supply, from easily obtaining and can independently storing this respect, is used kerosene as liquid fuel.
Reformer 2 has to liquid fuel is carried out steam reforming and generates the reformer 5 of reformed gas and the burner 6 that the reforming catalyst being housed in reformer 5 is heated.Burner 6 is used for promoting the reforming catalyst of steam reforming reaction by heating, will make catalyzed reaction effectively bring into play required heat supply in reforming catalyst.In reformer 5, the liquid fuel gasification importing from desulfurizer 3 and become unstripped gas, utilizes reforming catalyst to promote the steam reforming reaction between unstripped gas and water vapour (water), generates the reformed gas of rich hydrogen.
Fuel cell stack 4 is that a plurality of battery cells are piled up and the polymer electrolyte fuel cell storehouse of formation, uses the reformed gas obtaining at reformer 2 to generate electricity.Each battery cell there is anode, negative electrode and be configured in anode and negative electrode between the electrolytical macroion exchange membrane of conduct.In each battery cell, reformed gas is directed to anode and air is directed to negative electrode, carries out electrochemical electric power generation reaction.
Desulfurizer 3 comprises: the devulcanizer 8 that removes desulfuration composition from the liquid fuel being imported by pump 7; The liquid fuel that storage is discharged from devulcanizer 8 and the gas-liquid separation container 9 of gas (biogas and hydrogen etc.).For the amount of detected gas, in gas-liquid separation container 9, be provided with the floatswitch 11 of the liquid level of tracer liquid fuel.Gas-liquid separation container 9 is configured in the top of devulcanizer 8, and the liquid fuel of fuel and gas communication is, one end of gas communication pipeline 12 is connected with the diapire of devulcanizer 8 for liquid, and the other end is connected with the diapire of gas-liquid separation container 9.Thus, can will import in gas-liquid separation container 9 from devulcanizer 8 expellant gas reliably.
The roof of gas-liquid separation container 9 is connected with one end of gas outlet pipe line 13, and this gas outlet pipe line 13 is for discharging the gas that is stored in the top in gas-liquid separation container 9 from gas-liquid separation container 9.The other end of gas outlet pipe line 13 is connected with the burner 6 for the reforming catalyst of reformer 5 is heated.On gas outlet pipe line 13, be provided with the magnetic valve (open and close valve) 14 of the circulation that opens and closes gas. Magnetic valve 14 and 9 collaborative works of gas-liquid separation container, be configured for removing degasifier (degasser) D of gas from liquid fuel.And, in the downstream side of the magnetic valve 14 of gas outlet pipe line 13, be provided with the kapillary (throttle part) 15 that hinders gas communication.And the downstream side of the kapillary 15 of gas outlet pipe line 13 is connected with being provided with for air being imported to the circulation of air pipeline 17 of the pump 16 of burner 6.
On the other hand, the diapire of gas-liquid separation container 9 is connected with one end of liquid fuel vent line 18, and this liquid fuel vent line 18 is for discharging the liquid fuel that is stored in the below in gas-liquid separation container 9 from gas-liquid separation container 9.The other end of liquid fuel vent line 18 is connected with the sidewall of storage vessel 19 that is configured in the top of gas-liquid separation container 9.Liquid fuel within vent line 18 is provided with the kapillary 21 that hinders liquid fuel circulation.
The diapire of storage vessel 19 is connected with liquid fuel flow line 23, liquid fuel flow line 25, on this liquid fuel flow line 23, be provided with for by be stored in storage vessel 19 below liquid fuel import to the pump 22 of reformer 5, on this liquid fuel flow line 25, be provided with for this liquid fuel being imported to the pump 24 of burner 6.Like this, by liquid fuel is temporarily stored in storage vessel 19, can make the supply of liquid fuel of 22 pairs of reformers 5 of pump and the supply stabilization of the liquid fuel of 24 pairs of burners 6 of pump.
In the fuel cell system 1 forming as described above, first liquid fuel is directed in devulcanizer 8, in devulcanizer 8, utilizes desulfurization catalyst from liquid fuel, to remove desulfuration composition under the state of high temperature, high pressure.Liquid fuel and the gas of from devulcanizer 8, discharging are stored in gas-liquid separation container 9, and liquid fuel is directed in reformer 5 via liquid fuel vent line 18, storage vessel 19 and liquid fuel flow line 23.Now, liquid fuel is directed in burner via liquid fuel vent line 18, storage vessel 19 and liquid fuel flow line 25, and air is directed in burner 6 via circulation of air pipeline 17.Thus, in reformer 5, by the burner 6 heated reformate catalyzer that burn, use liquid fuel and generate reformed gas.The reformed gas generating in reformer 5 is directed in fuel cell stack 4, in fuel cell stack 4, uses reformed gas to generate electricity.
On the other hand, the gas being stored in gas-liquid separation container 9 is directed in burner 6 via gas outlet pipe line 13, is used as the fuel of burner 6 together with liquid fuel.Like this, can will from devulcanizer 8 expellant gas, effectively be used as the fuel of burner 6 together with liquid fuel.In addition, in the situation that magnetic valve 14 cuts out the circulation of gas, when the amount of the gas in the gas-liquid separation container 9 being detected by floatswitch 11 has surpassed specified amount, magnetic valve 14 is opened the circulation of gas several times.
As described above, in the desulfurizer 3 of fuel cell system 1, separated with liquid fuel gas-liquid separation container 9 from devulcanizer 8 expellant gas together with liquid fuel, via gas outlet pipe line 13, from gas-liquid separation container 9, be discharged from.The liquid fuel that therefore, can prevent from having sneaked into gas is fed into the back segment (for example, pump 22,24 and reformer 5 etc.) of desulfurizer 3.And, on gas outlet pipe line 13, in the downstream side of magnetic valve 14 that opens and closes the circulation of gas, be provided with the kapillary 15 that hinders gas communication.Therefore,, even the circulation for gas is opened to gas via gas outlet pipe line 13 from 9 discharges of gas-liquid separation container by magnetic valve 14, the reduction of the pressure in devulcanizer 8 also can be suppressed by kapillary 15, and is maintained at the state of high pressure.Therefore, adopt the desulfurizer 3 of fuel cell system 1, can prevent the detrimentally affect to back segment, and can from liquid fuel, remove reliably desulfuration composition.
And, utilizing and to be arranged on the kapillary 21 on liquid fuel vent line 18, the pressure decreased in devulcanizer 8 is also suppressed and be maintained at the state of high pressure.That is to say, because the pressure in devulcanizer 8 is maintained constantly by kapillary 15,21, therefore, pump 7 can use constant pressure pump.
And in the situation that magnetic valve 14 cuts out the circulation of gas, when the amount of the gas in the gas-liquid separation container 9 being detected by floatswitch 11 has surpassed specified amount, magnetic valve 14 is opened the circulation of gas several times.Thus, the pressure decreased in the devulcanizer 8 in the time of suppressing more reliably the circulation for gas is opened to gas from 9 discharges of gas-liquid separation container by magnetic valve 14 via gas outlet pipe line 13.
Figure 14 means the graphic representation of relation of the pressure of floatswitch, magnetic valve and devulcanizer in the fuel cell system of Figure 13.As shown in figure 14, floatswitch 11 is during ON, that is, the amount of the gas in gas-liquid separation container 9 surpasses (in this case 15 seconds) during specified amount, and with predetermined distance (in this case 5 seconds intervals), repeatedly (the in this case 3 times) short period of time (in this case 200m second) is opened magnetic valve 14.Thus, the pressure of the entrance and exit of devulcanizer 8 only produces pressure decreased (the in this case pressure decreased of 10～20kPa) a little, and is maintained high pressure.
The 4th technical scheme of the present invention is not limited to above-mentioned embodiment.
For example, fuel cell stack 4 is not limited to polymer electrolyte fuel cell storehouse, can be also Solid Oxide Fuel Cell storehouse etc.
And reformer 5 is not limited to the reformer of steam reforming, can be also that partial oxidation is reformed, the reformer of self thermal reforming.The reforming method of reformer 5 is based on outside kerosene, also according to gasoline, petroleum naphtha, light oil, methyl alcohol, ethanol, DME(dme), utilize the reforming method of characteristic of the liquid fuels such as biofuel of biological substance.
And the throttle part of the throttle part of the obstruction gas communication on gas outlet pipe line 13, the circulation of the obstruction liquid fuel on liquid fuel vent line 18 is not limited to kapillary 15,21, also can utilize throttle orifice, needle type valve etc.
the 5th embodiment
Below with reference to Figure 15～Figure 21, the fuel cell system 1 of the 5th embodiment is described in detail.
As shown in figure 15, fuel cell system 1 comprises: the desulfurizer 2 that removes desulfuration composition from the crude fuel of supplying with; To having been removed by desulfurizer 2 that the liquid fuel of sulphur composition is reformed and the reformer 3 that generates reformed gas; The fuel cell stack 4 that the reformed gas that use is generated by reformer 3 generates electricity.Fuel cell system 1, for example as home-use power supply, from easily obtaining and can independently storing this respect, is used kerosene as crude fuel.
Reformer 3 has to liquid fuel is carried out steam reforming and generates the reformer 5 of the reformed gas of rich hydrogen, the burner 6 that the reforming catalyst being housed in reformer 5 is heated.Burner 6 is used for promoting the reforming catalyst of steam reforming reaction by heating, will make catalyzed reaction effectively bring into play required heat supply in reforming catalyst.The fuel of burner 6 is mainly crude fuel and oxygen.Therefore, burner 6 and burning line 25 for supplying with crude fuel with for air being imported to the circulation of air pipeline 17 that the gas blower 16 of burner 6 is connected, be connected.In reformer 5, by desulfurizer 2, carried out the liquid fuel gasification of desulfurization and become unstripped gas, utilize reforming catalyst to promote the steam reforming reaction between unstripped gas and water vapour (water), generate the reformed gas of rich hydrogen.
Fuel cell stack 4 is that a plurality of battery cells are piled up and the polymer electrolyte fuel cell storehouse of formation, uses the reformed gas obtaining at reformer 3 to generate electricity.Each battery cell there is anode, negative electrode and be configured in anode and negative electrode between the electrolytical macroion exchange membrane of conduct.In each battery cell, reformed gas is directed to anode and air is directed to negative electrode, carries out electrochemical electric power generation reaction.
Desulfurizer 2 comprises: the devulcanizer 8 that removes desulfuration composition from the crude fuel being imported by constant pressure pump 7; For separating of the liquid fuel of discharging from devulcanizer 8 and the gas-liquid separation container 9 of gas (biogas and hydrogen etc.).Crude fuel comprises the sulphur compositions such as sulphur below about 80ppm and sulfide.Devulcanizer 8 is except desulfuration composition from crude fuel, and generating sulphur concentration is the liquid fuel below about 50ppb.Devulcanizer 8 is interior is remained on high pressure conditions by structure described later, carries out desulphurization reaction under high pressure conditions.
For the amount of detected gas at the interior floatswitch 11 that the liquid level of tracer liquid fuel is set of gas-liquid separation container 9.Gas-liquid separation container 9 is configured in the top of devulcanizer 8, and the liquid fuel of fuel and gas communication is, one end of gas communication pipeline 12 is connected with the diapire of devulcanizer 8 for liquid, and the other end is connected with the diapire of gas-liquid separation container 9.Thus, can will import in gas-liquid separation container 9 from devulcanizer 8 expellant gas reliably.The volume of this gas-liquid separation container 9 is 100cc left and right.In addition, though not shown, in order to remove the desulfurization catalyst comprising in the liquid fuel of having removed sulphur composition by devulcanizer 8, on liquid fuel within, gas communication pipeline 12, strainer is set.In the 5th embodiment, for example, can use mesh is the strainer of 0.026mm left and right.
The roof of gas-liquid separation container 9 is connected with one end of gas outlet pipe line 13, and this gas outlet pipe line 13 is for discharging the gas that is stored in the top in gas-liquid separation container 9 from gas-liquid separation container 9.On gas outlet pipe line 13, be provided with the magnetic valve 14 of the circulation that opens and closes gas. Magnetic valve 14 and 9 collaborative works of gas-liquid separation container, form the degasifier D that removes gas from liquid fuel.And the downstream side of the magnetic valve 14 on gas outlet pipe line 13 is provided with the kapillary 15 that hinders gas communication.Therefore,, even the circulation for gas is opened to gas via gas outlet pipe line from the discharge of gas-liquid separation container by magnetic valve 14, the reduction of the pressure in devulcanizer 8 and gas-liquid separation vessel 9 also can be suppressed by kapillary 15.And the downstream side of the kapillary 15 on gas outlet pipe line 13 is connected with circulation of air pipeline 17.
On the other hand, the diapire of gas-liquid separation container 9 is connected with one end of liquid fuel vent line 18, and this liquid fuel vent line 18 is for discharging the liquid fuel that is stored in the below in gas-liquid separation container 9 from gas-liquid separation container 9.The other end of liquid fuel vent line 18 is connected with the diapire of storage vessel 19 that is configured in the top of gas-liquid separation container 9.On this liquid fuel vent line 18, be provided with the kapillary 21 that hinders liquid fuel circulation.
At this, kapillary 21 is wound into spirrillum by superfine pipe and forms.Kapillary 21 carries out throttling in the downstream side of devulcanizer 8 to the flow of liquid fuel, and therefore can make the flow in devulcanizer 8 is low flow.On the other hand, by constant pressure pump 7, to the interior positive delivery liquid fuel of devulcanizer 8, so devulcanizer 8 is interior pressurized, under high pressure carries out desulphurization reaction.For example, in the situation that the fuel cell system of 1kW, the internal diameter of kapillary 21 and the diameter while being wound are set to, the flow that makes liquid fuel (liquid fuel) is below 10g/min, and the stream internal pressure from constant pressure pump 7 to kapillary 21 is to be greater than the high pressure that 0.1MPa is less than or equal to 1.0MPa.Specifically, the internal diameter of refin tubule 21 is 0.1mm～0.5mm left and right, and the diameter that is preferably wound into spiral is 10mm～100mm left and right.
As mentioned above, liquid fuel within, gas communication pipeline 12 are provided with strainer, but the little desulfurization catalyst of particle diameter ratio mesh can pass through strainer, therefore, when the not enough 0.lmm of internal diameter of kapillary 21, exist kapillary 21 to be easily desulfurized the tendency that catalyzer stops up.On the other hand, when the internal diameter of kapillary 21 surpasses 0.5mm, exist and be difficult to the tendency with low flow transporting liquid fuel.In addition, the size of the diameter while being wound according to kapillary 21, can adjust crushing.
The downstream side of the kapillary 21 on liquid fuel within vent line 18 is provided with under meter 26.Under meter 26 is measured the flow of the liquid fuel flowing out from kapillary 21.That is, under meter 26 is measured the formation speed of the liquid fuel being generated by the desulphurization reaction in devulcanizer 8.This under meter 26 is arranged on the downstream side of gas-liquid separation container 9, and what therefore measure is the flow of the separated rear liquid fuel flowing into of gas, stably measuring flow.
Desulfurizer 2 also has the oil storage vessel 19 that is connected with liquid fuel vent line 18 and is configured in the downstream side of under meter 26.The roof of oil storage vessel 19 is connected with liquid fuel flow line 23, is provided with for being stored in liquid fuel in oil storage vessel 19 and outputing to the Send out pump 24 of reformer 5 on this liquid fuel flow line 23.The roof of oil storage vessel 19 also with for the gas expellant gas vent line 27 that is stored in the top in oil storage vessel 19 is connected.
Then,, with reference to Figure 16 and Figure 17, oil storage vessel 19 is described in detail.Oil storage vessel 19 is the hollow rectangular-shaped containers that consist of roof 19a, diapire 19b, sidewall 19c, and volume is 200cc left and right.On oil storage vessel 19, linking inflow pipe 31, on these inflow pipe 31 liquid fuel within vent lines 18, kapillary 21 and oil storage vessel 19 are being linked up.Inflow pipe 31 runs through diapire 19b, and the influx 31a that is positioned at oil storage vessel 19 of inflow pipe 31 is opening upward.From this influx 31a to the interior inflow of oil storage vessel 19, there is the liquid fuel of high pressure.
On the roof 19a of oil storage vessel 19, be provided with venting hole 32, the one end that forms the vapor pipe 33 of gas outlet pipe line 27 is inserted in venting hole 32.The other end of this vapor pipe 33 is towards atmosphere opening, so the pressure in oil storage vessel 19 is retained as normal atmosphere, from the liquid fuel flowing into, isolates the gas being contained in this liquid fuel.In oil storage vessel 19, from liquid fuel, isolated gas flows into vapor pipe 33 from venting hole 32, from the other end of vapor pipe 33, is discharged from.The other end of vapor pipe 33 is configured near the suction port of gas blower 16, so gas sucked by gas blower 16, is utilized as the combustion fuel of burner 6.
In oil storage vessel 19, be provided with the outlet pipe 34 that Send out pump 24 and oil storage vessel 19 is linked up and formed a part for liquid fuel flow line 23.This Send out pump 24 is normal pressure pumps, for example, be that outlet pressure is the pump of 100kPa left and right.Outlet pipe 34 runs through roof 19a and is inserted in oil storage vessel 19, and the spout 34a that is positioned at oil storage vessel 19 of outlet pipe 34 is opening downwards.By the work of Send out pump 24, the liquid fuel in oil storage vessel 19 is sent in reformer 5 via outlet pipe 34.
The control water level S of the liquid fuel in oil storage vessel 19 is controlled by float-actuated valve 35.Float 36 on one end that is installed in arm of float-actuated valve 35 floats on liquid level, and in the situation that liquid level is lower than control water level S, as shown in figure 16, liquid fuel flow in oil storage vessel 19 from the influx 31a of inflow pipe 31.When liquid level reaches water level S, as shown in figure 17, the stopper (tap) 37 being installed on the other end of arm is embedded in inflow pipe 31 influx 31a, and the stream in inflow pipe 31 is closed.
Flow into the catalyst plate 38 of sneaking into the desulfurization catalyst in devulcanizer 8 in the liquid fuel in oil storage vessel 19.By liquid fuel being stored in oil storage vessel 19, the catalyst plate 38 of this desulfurization catalyst, in the interior sinking of oil storage vessel 19, is accumulated in the bottom of oil storage vessel 19.That is, the bottom of oil storage vessel 19 as accumulate desulfurization catalyst catalyst plate 38 catalyst plate reservoir 39 and play a role.The catalyst plate 38 of this desulfurization catalyst brings detrimentally affect to the equipment of back segment, and therefore, for it is not flowed out from outlet pipe 34, spout 34a is positioned at the top of catalyst plate reservoir 39.And in order to make not roll from the liquid fuel of inflow pipe 31 inflows the catalyst plate 38 of desulfurization catalyst, influx 31a is positioned at the top of catalyst plate reservoir 39.
For the catalyst plate 38 that is accumulated in the desulfurization catalyst in this catalyst plate reservoir 39 is discharged from oil storage vessel 19, the diapire of oil storage vessel 19 and vent pipe 40 are connected.On vent pipe 40, clamped magnetic valve 41, by opening magnetic valve 41, can easily the catalyst plate 38 being accumulated in during magnetic valve 41 is closed in catalyst plate reservoir 39 have been discharged.
In the fuel cell system 1 forming as described above, first crude fuel is directed in devulcanizer 8, in devulcanizer 8, utilizes desulfurization catalyst from liquid fuel, to remove desulfuration composition under the state of high temperature, high pressure.The liquid fuel being discharged from from devulcanizer 8 and gas carry out separatedly by being stored in gas-liquid separation container 9, liquid fuel is directed in liquid fuel vent line 18.In the flow liquid fuel within vent line 18 of liquid fuel, in kapillary 21 downstream sides, utilize under meter 26 to measure, liquid fuel flows in oil storage vessel 19.The liquid fuel of high pressure flows in the oil storage vessel 19 that is retained as normal pressure, thereby separated in gas from liquid fuel.Then, liquid fuel utilizes Send out pump 24 to be directed in reformer 5 via liquid fuel flow line 23 after being stored in oil storage vessel 19.And gas is discharged via gas outlet pipe line 27 in oil storage vessel 19, utilize gas blower 16 to supply with to burner 6, as fuel, use.
On the other hand, crude fuel is directed in burner 6 via burning line 25, and air is mainly directed in burner 6 via circulation of air pipeline 17.Thus, in reformer 5, burner 6 heating that reforming catalyst is burnt, generate reformed gas by liquid fuel.The reformed gas generating in reformer 5 is directed in fuel cell stack 4, and fuel cell stack 4 is used reformed gas to generate electricity.
On the other hand, the gas being stored in gas-liquid separation container 9 is directed in burner 6 via gas outlet pipe line 13, is used as the fuel of burner 6 together with liquid fuel.In addition, magnetic valve 14 is in the situation that the circulation of confining gas, and when the amount of the gas in the gas-liquid separation container 9 being detected by floatswitch 11 has surpassed specified amount, magnetic valve 14 is opened the circulation of gas several times.
In oil storage vessel 19, the liquid level of liquid fuel reaches while controlling water level S, and by the influx 31a of float-actuated valve 35 sealing inflow pipes 31, liquid fuel stops to the inflow in oil storage vessel 19.When the liquid level of liquid fuel within is lower than control water level S, opened the influx 31a of inflow pipe 31 by float-actuated valve 35, liquid fuel starts to the interior inflow of oil storage vessel 19.
And, when catalyst plate 38 is accumulated in the catalyst plate reservoir 39 of oil storage vessel 19, by opening the magnetic valve 41 being arranged on vent pipe 40, catalyst plate 38 is discharged from oil storage vessel 19.Opening also of magnetic valve 41 can be set to specific time interval and carry out.
In the fuel cell system 1 of the present embodiment as above illustrating, the oil storage vessel 19 of storage liquid fluid fuel is configured between devulcanizer 8 and reformer 5, is provided with the venting hole 32 towards atmosphere opening on this oil storage vessel 19.Therefore, crude fuel under high pressure carries out desulfurization in devulcanizer 8, and the liquid fuel being desulfurized flows in oil storage vessel 19, and is contained in gas in liquid fuel by venting hole 32 and from the interior discharge of oil storage vessel 19.Because the gas being contained in liquid fuel is discharged, therefore, can be increased in the flow measurement of liquid fuel and the reliability of flow control in oil storage vessel 19 downstream sides.Therefore, can control reliably the flow that flow into the liquid fuel in reformer 19, the reduction of the performance that can prevent from reforming.And the liquid fuel of high pressure conditions does not flow into the downstream side of oil storage vessel 19, therefore do not need the equipment that adapts to high pressure phase, can improve the weather resistance of the back segment equipment of oil storage vessel 19, can realize low cost.
And the fuel cell system 1 of the 5th embodiment comprises: with constant voltage, crude fuel is pressed and delivered to the constant pressure pump 7 in devulcanizer 8; Be configured in the kapillary 21 of the downstream side of devulcanizer 8 and the upstream side of oil storage vessel 19.Therefore, crude fuel flow in devulcanizer 8 with constant voltage, on the other hand, from the discharge of devulcanizer 8 by throttling.Therefore, do not use the pump of high price, just can make the pressure ratio normal atmosphere in devulcanizer high, and can the flow of crude fuel (liquid fuel) be kept lowlyer.
And, in the fuel cell system 1 of the 5th embodiment, separated with liquid fuel gas-liquid separation container 9 from devulcanizer 8 expellant gas together with liquid fuel, via gas outlet pipe line 13, from gas-liquid separation container 9, discharge.On gas outlet pipe line 13, in the downstream side that opens and closes the magnetic valve 14 of gas communication, be provided with the kapillary 15 that hinders gas communication.Therefore,, even the circulation for gas is opened to gas via gas outlet pipe line 13 from 9 discharges of gas-liquid separation container by magnetic valve 14, the reduction of the pressure in devulcanizer 8 also can be suppressed by kapillary 15.Therefore, the pressure in devulcanizer 8 can be held in to high pressure, can be reliably except desulfuration composition from crude fuel.On the other hand, liquid fuel flow in oil storage vessel 19 via liquid fuel vent line 18.Because liquid fuel within vent line 18 is provided with under meter 26, the flow of the liquid fuel that therefore can stably measure separated from the gas.
And, in the fuel cell system 1 of the 5th embodiment, the catalyst plate 38 for desulfurization flowing out can be accumulated in to the catalyst plate reservoir 39 that is positioned at oil storage vessel 19 bottoms together with liquid fuel from devulcanizer 8, make in its reformer that does not flow into back segment 5.And, the influx 31a of the liquid fuel in oil storage vessel 19 and spout 34a are positioned at the top of catalyst plate reservoir 39, therefore, can suppress the catalyzer that inflow and outflow due to liquid fuel make to be accumulated in catalyst plate reservoir 39 flies upward, from storage tanks 19, flow in reformer 5.
In general, in the situation that extract out being accumulated in liquid in container with pump, this spout is arranged on the below of container for air amount not.In the fuel cell system 1 of the 5th embodiment, by spout 34a being arranged on to the top of catalyst plate reservoir 39, the catalyzer that can suppress to be accumulated in catalyst plate reservoir 39 flies upward, from storage tanks 19, flows out and flow in reformer 5.
And, in the fuel cell system 1 of the 5th embodiment, thering is the burner 6 of heated reformate device 5, this burner 6 is the fuel as burning use by the eluting gas flowing out from venting hole 32.Therefore, can prevent that the eluting gas flowing out from venting hole 32 from flowing out to fuel cell system 1 around.And, due to the fuel that uses eluting gas as burner 6, so can contribute to energy-conservation.
Above the preferred embodiments of the 5th technical scheme of the present invention is described in detail, but the 5th technical scheme of the present invention can be carried out various distortion.
As shown in figure 18, also degasifier D, gas outlet pipe line 13 can be set in fuel cell system 1.As fuel cell system la, also can utilize liquid fuel, gas communication pipeline 12 that devulcanizer 8 and oil storage vessel 19 are directly coupled together, liquid fuel within, gas communication pipeline 12 are provided with kapillary 21.
And, in the 5th embodiment, in order to control the water level in oil storage vessel 19, float-actuated valve 35 is set, but is not limited to this.As shown in Figure 19 and Figure 20, substitute float-actuated valve 35, fuel cell system 1 also can comprise: the liquid level that detects the liquid fuel in oil storage vessel 19 reaches the low water level sensor 51 of low-water level S1; The liquid level that detects the liquid fuel in oil storage vessel 19 reaches the high water level sensor 52 of high-water S2; The control part 53 of controlling according to the output signal of this low water level sensor 51 and high water level sensor 52.As this low water level sensor 51 and high water level sensor 52, such as using floatswitch, electrode type water level sensor, pressure type water level sensor etc.
In this case, be provided with magnetic valve 42 on inflow pipe 31, the open and close controlling portion 54 that the switching of this magnetic valve 42 is had by control part 53 controls.And control part 53 comprises: to detecting low-water level S1 from low water level sensor 51 until the timing register 55 measured of the time that high water level sensor 52 detects high-water S2; The operational part 56 of the flow of the Measuring Time computing liquid fuel based on timing register 55; Operation result based on operational part 56 carries out the pump control part 57 of the control of constant pressure pump 7.
When the liquid level of the liquid fuel in oil storage vessel 19 reaches low-water level S1 from the state higher than low-water level S1, the liquid level that utilizes low water level sensor 51 liquid fuel to be detected has reached low-water level S1, from low water level sensor 51 to control part 53 output electrical signals.When the electrical signal of exporting from low water level sensor 51 is input to open and close controlling portion 54, open and close controlling portion 54 opens magnetic valve 41 from closing condition, and liquid fuel starts to flow in oil storage vessel 19.
When the liquid level of the liquid fuel in oil storage vessel 19 reaches high-water S2 from the state lower than high-water S2, the liquid level that utilizes high water level sensor 52 liquid fuel to be detected has reached high-water S2, from high water level sensor 52 to control part 53 output electrical signals.When the electrical signal of exporting from high water level sensor 52 is input to open and close controlling portion 54, open and close controlling portion 54 closes magnetic valve 41 from open mode, and liquid fuel stops to the inflow in oil storage vessel 19.
On the other hand, from the electrical signal of low water level sensor 51 outputs and the electrical signal of exporting from high water level sensor 52, be input to respectively timing register 55.The time of 55 pairs of electrical signal that the electrical signal from low water level sensor 51 outputs is exported from high water level sensor 52 to input from input of timing register measures, and the electrical signal that represents this Measuring Time is outputed to operational part 56.When operational part 56 inputs have from the electrical signal of the expression Measuring Time of timing register 55, based on this Measuring Time, calculate the flow of liquid fuel.Operational part 56 outputs to pump control part 57 by the electrical signal of the flow that represents to calculate.When 57 inputs of pump control part have from the electrical signal of the expression flow of operational part 56, the driving based on this flow control constant pressure pump 7.
In this case, water level sensor utilizes timing register to measure to the time that detects high-water detecting low-water level, and the Measuring Time of arithmetic facility based on timing register calculated the flow of liquid fuel, therefore does not need to arrange in addition under meter.Thus, can seek more cost degradation.
And the influx 31a of the liquid fuel in oil storage vessel 19 and spout 34a are positioned at the below of low-water level S1, therefore, in the time of preventing liquid fuel within inflow, liquid fuel bubbles, and can prevent from when liquid fuel within from flowing out being involved in air from underwater outflow.
In addition, the flow of liquid fuel, the output of Send out pump 24 etc. that the outlet pipe 34 that operational part 56 also can be based on from oil storage vessel 19 flows out are calculated liquid fuel and are flowed into the flow in oil storage vessel 19.And pump control part 57 also can the Measuring Time based on timing register 55 carry out the driving control of constant pressure pump 7.
And as shown in figure 21, the variation as the fuel cell system 1 of the 5th embodiment also can link upflow tube 43 on oil storage vessel 19.One end of this upflow tube 43 is through the roof of oil storage vessel 19, and an opening 43a is configured in the position M higher than the water level S in oil storage vessel 19, downwards opening.Upflow tube 43 is along the outside configuration of the sidewall 19c of oil storage vessel 19, and another opening 43b is positioned at the outside of oil storage vessel 19, downwards opening.Therefore,, even because some reason liquid fuel such as fault of float-actuated valve 35 riddles in oil storage vessel 19, liquid fuel also can utilize upflow tube 43 to discharge from oil storage vessel 19.
Below oil storage vessel 19, dispose food tray 44, from the liquid fuel that another opening 43b of the upflow tube 43 of opening discharges downwards, flow in food tray 44.When liquid fuel flows into food tray 44 when interior, by being configured in leak sensor 45 on the bottom surface of food tray 44, detecting liquid fuel and escaped in food tray 44.In this case, control device (not shown), according to the input of the detection signal of leak sensor 45, makes the work of constant pressure pump 7 stop the control waiting, thereby the supply of energy stop liquid fuel stops the outflow of liquid fuel.
In addition, upflow tube is not limited to aforesaid way, also can form linearity.In this case, upflow tube is configured to: from the opening of the diapire 19b of oil storage vessel 19, insert, one end is configured in the position of the height that is set in the full-water level in oil storage vessel 19, and the other end is positioned at the below of the diapire 19b outside oil storage vessel 19, towards food tray 44 openings.
And the fuel cell system of the 5th embodiment can carry out various distortion.Fuel cell stack 4 is not limited to polymer electrolyte fuel cell storehouse, can be also Solid Oxide Fuel Cell storehouse etc.Except kerosene, can also utilize gasoline, petroleum naphtha, light oil, methyl alcohol, ethanol, DME(dme), utilize the liquid fuels such as biofuel of biological substance as crude fuel.And reformer 5 is not limited to carry out the reformer of steam reforming, it can be also the reformer that carries out partial oxidation reformation, self thermal reforming.And, also can use constant flow pump to substitute constant pressure pump 7.But the stress management aspect in devulcanizer 8, is preferably used constant pressure pump 7.
the 6th embodiment
Below with reference to Figure 22 and Figure 23, the fuel cell system 1 of the 6th embodiment is described in detail.
As shown in figure 22, fuel cell system 1 comprises: the reformer 2 that generates the reformed gas that contains hydrogen; From will be supplied to the liquid fuel reformer 2, remove the desulfurizer 3 of desulfuration composition; The fuel cell stack 4 that the reformed gas that use is generated by reformer 2 generates electricity.Fuel cell system 1, for example as home-use power supply, from easily obtaining and can independently storing this respect, is used kerosene as liquid fuel.In addition, the part except fuel cell stack 4 in fuel cell system 1 (reformer 2, desulfurizer 3 and pump described later 16,22,24) forms reforming system R.
Reformer 2 has to liquid fuel is carried out steam reforming and generates the reformer 5 of reformed gas, the burner 6 that the reforming catalyst being housed in reformer 5 is heated.Burner 6 is used for promoting the reforming catalyst of steam reforming reaction by heating, will make catalyzed reaction effectively bring into play required heat supply in reforming catalyst.In reformer 5, the liquid fuel gasification importing from desulfurizer 3 and become unstripped gas, utilizes reforming catalyst to promote the steam reforming reaction between unstripped gas and water vapour (water), generates the reformed gas of rich hydrogen.
Fuel cell stack 4 is that a plurality of battery cells are piled up and the polymer electrolyte fuel cell storehouse of formation, uses the reformed gas obtaining at reformer 2 to generate electricity.Each battery cell there is anode, negative electrode and be configured in anode and negative electrode between the electrolytical macroion exchange membrane of conduct.In each battery cell, reformed gas is directed to anode and air is directed to negative electrode, carries out electrochemical electric power generation reaction.
Desulfurizer 3 comprises: the devulcanizer 8 that removes desulfuration composition from the liquid fuel being imported by constant pressure pump 7; The gas-liquid separation container 9 that the liquid fuel of discharging from devulcanizer 8 and gas (biogas and hydrogen etc.) are stored.For the amount of detected gas, in gas-liquid separation container 9, be provided with the floatswitch 11 of the liquid level of tracer liquid fuel.Gas-liquid separation container 9 is configured in the top of devulcanizer 8, and the liquid fuel of feeding liquid fuel and gas communication, one end of gas communication pipeline 12 are connected with the diapire of devulcanizer 8, and the other end is connected with the diapire of gas-liquid separation container 9.Thus, can will import in gas-liquid separation container 9 from devulcanizer 8 expellant gas reliably.In addition, though not shown, in order to remove the desulfurization catalyst being contained in the liquid fuel of having removed sulphur composition by devulcanizer 8, liquid fuel within, gas communication pipeline 12 are provided with strainer.In the present embodiment, for example can use mesh for the strainer of 0.026mm left and right.
The roof of gas-liquid separation container 9 is connected with one end of gas outlet pipe line 13, and this gas outlet pipe line 13 is for discharging the gas that is stored in the top in gas-liquid separation container 9 from gas-liquid separation container 9.The other end of gas outlet pipe line 13 is connected with the burner 6 that the reforming catalyst of reformer 5 is heated.On gas outlet pipe line 13, be provided with the magnetic valve 14 of the circulation that opens and closes gas. Magnetic valve 14 and 9 collaborative works of gas-liquid separation container, form the degasifier D that removes gas from liquid fuel.And the downstream side of the magnetic valve 14 on gas outlet pipe line 13 is provided with the kapillary 15 that hinders gas communication.And the downstream side of the kapillary 15 on gas outlet pipe line 13 is connected with being provided with for air being imported to the circulation of air pipeline 17 of the pump 16 of burner 6.
On the other hand, the diapire of gas-liquid separation container 9 is connected with one end of liquid fuel vent line 18, and this liquid fuel vent line 18 is for discharging the liquid fuel that is stored in the below in gas-liquid separation container 9 from gas-liquid separation container 9.The other end of liquid fuel vent line 18 is connected with the sidewall of storage vessel 19 that is configured in the top of gas-liquid separation container 9.Liquid fuel within vent line 18 is provided with the kapillary 21 that hinders liquid fuel circulation.
At this, kapillary 21 is wound into spirrillum by superfine pipe and forms.The internal diameter of kapillary 21 and the diameter while being wound are set to, and make under the pressure being determined by constant pressure pump, and the flow of liquid fuel is low flow (being for example, below 10g/min when the fuel cell system of 1kW).Specifically, the internal diameter of refin tubule 21 is 0.1mm～0.7mm left and right, and the diameter that is preferably wound into spiral is 10mm～100mm left and right.The total length of kapillary 21 is about 600mm in the 6th embodiment, but can consider the flow of needs, the diameter when internal diameter of the pressure in the devulcanizer 8 of needs, kapillary 21 and coiling kapillary 21 is set.As mentioned above, although liquid fuel within, gas communication pipeline 12 are provided with strainer, the desulfurization catalyst that particle diameter ratio mesh is little can pass through strainer, therefore, when the not enough 0.lmm of the internal diameter of kapillary 21, exist desulfurization catalyst easily to stop up the tendency of kapillary 21.On the other hand, when the internal diameter of kapillary 21 surpasses 0.7mm, in order to be maintained high pressure in devulcanizer 8 and to carry out the conveying of liquid fuel with low flow, make the total length of the kapillary 21 that needs elongated, have the tendency that is difficult to miniaturization.In addition, the size of the diameter while being wound according to kapillary 21, can adjust crushing.
The diapire of storage vessel 19 is connected with liquid fuel flow line 23, liquid fuel flow line 25, this liquid fuel flow line 23 is provided with for the liquid fuel that is stored in the below in storage vessel 19 being imported to the pump 22 of reformer 5, and this liquid fuel flow line 25 is provided with for this liquid fuel being imported to the pump 24 of burner 6.Like this, by liquid fuel is temporarily stored in storage vessel 19, can make the supply of liquid fuel of 22 pairs of reformers 5 of pump and the supply stabilization of the liquid fuel of 24 pairs of burners 6 of pump.
In the fuel cell system 1 forming as described above, first liquid fuel is directed in devulcanizer 8, in devulcanizer 8, utilizes desulfurization catalyst from liquid fuel, to remove desulfuration composition under the state of high temperature, high pressure.Liquid fuel and the gas of from devulcanizer 8, discharging are stored into gas-liquid separator 9, and liquid fuel is directed in reformer chamber 5 via liquid fuel vent line 18, storage vessel 19 and liquid communication pipeline 23.Now, liquid fuel is directed in burner 6 via liquid fuel vent line 18, storage vessel 19 and liquid communication pipeline 25, and air is directed in burner 6 via circulation of air pipeline 17.Thus, in reformer 5,6 heating of burner that reforming catalyst is burnt, are used liquid fuel and generate reformed gas.The reformed gas generating in reformer 5 is directed in fuel cell stack 4, in fuel cell stack 4, uses reformed gas to generate electricity.
On the other hand, the gas being stored in gas-liquid separation container 9 is directed in burner 6 via gas outlet pipe line 13, is used as the fuel of burner 6 together with liquid fuel.Like this, can effectively utilize together with liquid fuel the fuel as burner 6 from devulcanizer 8 expellant gas.In addition, magnetic valve 14 is in the situation that cut out the circulation of gas, and when the amount of the gas in the gas-liquid separation container 9 being detected by floatswitch 11 has surpassed specified amount, magnetic valve 14 is opened the circulation of gas several times.
In the 6th embodiment as described above, kapillary 21 is configured in to the downstream side of devulcanizer 8.Therefore, by suitably selecting internal diameter and the length of kapillary 21, do not use the pump of high price, the size of the flow that just can make pressure in devulcanizer 8 and liquid fuel for expecting.Its result, can be easy and realize at low cost carrying the liquid fuel of low flow.
It is generally acknowledged also and can utilize the alternative kapillaries 21 such as throttle orifice, needle type valve.But, there is the limit in the stream that extends throttle orifice part, therefore for the flow of the liquid fuel of the high pressure that reduces to be discharged from from devulcanizer 8, has to make the diameter of throttle orifice part very little.At this, in devulcanizer 8, utilize desulfurization catalyst to carry out the desulfurization of liquid fuel, but desulfurization catalyst is contained in and utilize devulcanizer 8 to remove in the liquid fuel of sulphur composition sometimes.Therefore,, in the situation that having utilized throttle orifice, needle type valve etc., the desulfurization catalyst flowing out from devulcanizer 8 stops up the stream of throttle orifice part sometimes.
But, in the fuel cell system 1 of the 6th embodiment, use as described above kapillary 21, therefore, according to the length of kapillary 21, can increase to a certain extent the internal diameter of kapillary 21.The situation of the obstruction that therefore, extremely difficult generation is caused by desulfurization catalyst.
Above the preferred embodiments of the 6th technical scheme of the present invention is explained, but the 6th technical scheme of the present invention is not limited to above-mentioned embodiment.For example, fuel cell stack 4 is not limited to polymer electrolyte fuel cell storehouse, can be also Solid Oxide Fuel Cell storehouse etc.
And reformer 5 is not limited to the reformer of steam reforming, can be also that partial oxidation is reformed, the reformer of self thermal reforming.The reforming method of reformer 5 is based on outside kerosene, also according to gasoline, petroleum naphtha, light oil, methyl alcohol, ethanol, DME(dme), utilize the reforming method of characteristic of the liquid fuels such as biofuel of biological substance.
And, also can use constant flow pump to substitute constant pressure pump 7.But the stress management aspect in devulcanizer 8, is preferably used constant pressure pump 7.
And, as shown in figure 23, can at fuel cell system 1, degasifier D, gas outlet pipe line 13 and kapillary 15 be set yet.That is, also can utilize liquid fuel, gas communication pipeline 12 that devulcanizer 8 and storage vessel 19 are directly coupled together, on liquid fuel within, gas communication pipeline 12, kapillary 21 is set.In addition, now, pump 16 and burner 6 directly couple together by circulation of air pipeline 17.

Claims (15)

1. a reforming system, is characterized in that, this reforming system comprises:
Pump, it is for sending liquid fuel;
Devulcanizer, it is configured in the downstream side of said pump, for removing desulfuration composition from aforesaid liquid fuel;
Kapillary, it is configured in the downstream side of above-mentioned devulcanizer, for the liquid fuel that utilizes above-mentioned devulcanizer to remove sulphur composition, passes through,
Reformer, it is configured in above-mentioned downstream side capillaceous, uses the liquid fuel that utilizes above-mentioned devulcanizer to remove sulphur composition to generate the reformed gas that contains hydrogen.
2. reforming system according to claim 1, is characterized in that,
Said pump is constant pressure pump.
3. reforming system according to claim 1, is characterized in that,
Above-mentioned internal diameter capillaceous is 0.lmm～0.7mm.
4. reforming system according to claim 1, is characterized in that,
Above-mentioned kapillary is wound into spirrillum.
5. a fuel cell system, is characterized in that, this fuel cell system comprises:
Devulcanizer, it for generating liquid fuel from the crude fuel of liquid except desulfuration composition under higher than atmospheric pressure;
Oil storage vessel, it is provided with the venting hole towards atmosphere opening, for storing the aforesaid liquid fuel of discharging from above-mentioned devulcanizer;
Send out pump, it for sending aforesaid liquid fuel in above-mentioned oil storage vessel;
Reformer, it is configured in the downstream side of above-mentioned Send out pump, for aforesaid liquid fuel is reformed and generated reformed gas;
Fuel cell stack, it uses above-mentioned reformed gas to generate electricity.
6. fuel cell system according to claim 5, is characterized in that, this fuel cell system comprises:
Constant pressure pump, it is pressed and delivered to above-mentioned crude fuel in above-mentioned devulcanizer with constant voltage;
Kapillary, the upstream side that it is configured in the downstream side of above-mentioned devulcanizer and is configured in above-mentioned oil storage vessel.
7. fuel cell system according to claim 6, is characterized in that, this fuel cell system comprises:
Gas-liquid separation container, it is for by aforesaid liquid fuel and the gas delivery of discharging from above-mentioned devulcanizer;
Liquid fuel vent line, it is for discharging aforesaid liquid fuel from above-mentioned gas-liquid separation container;
Gas outlet pipe line, it is for discharging above-mentioned gas from above-mentioned gas-liquid separation container;
Open and close valve, it is located on above-mentioned gas vent line, for opening and closing the circulation of above-mentioned gas;
Throttle part, it is arranged on the downstream side of the above-mentioned open and close valve of above-mentioned gas vent line, for hindering above-mentioned gas circulation,
Under meter, it is located on aforesaid liquid fuel discharge pipe line,
Above-mentioned kapillary is located at the upstream side of the above-mentioned under meter on aforesaid liquid fuel discharge pipe line,
Downstream side and the aforesaid liquid fuel discharge pipe line of the above-mentioned under meter of above-mentioned oil storage vessel on aforesaid liquid fuel discharge pipe line are connected.
8. fuel cell system according to claim 5, is characterized in that, this fuel cell system comprises:
Water level sensor, it is for detection of low-water level and the high-water of the aforesaid liquid fuel in above-mentioned oil storage vessel;
Timing register, it detects above-mentioned low-water level to the time that above-mentioned high-water detected for measuring from above-mentioned water level sensor;
Arithmetic facility, its Measuring Time based on above-mentioned timing register, calculates the flow of aforesaid liquid fuel.
9. fuel cell system according to claim 5, is characterized in that,
The effect of catalyst plate reservoir is played in the bottom of above-mentioned oil storage vessel, and it is for accumulating together with aforesaid liquid fuel the desulfurization catalyst sheet flowing into from above-mentioned devulcanizer,
The influx of the aforesaid liquid fuel in above-mentioned oil storage vessel and spout are positioned at the top of above-mentioned catalyst plate reservoir.
10. fuel cell system according to claim 5, is characterized in that, this fuel cell system comprises:
Food tray, it is configured in the below of above-mentioned oil storage vessel;
Upflow tube, one opening is configured in above-mentioned oil storage vessel, another opening be configured in above-mentioned oil storage vessel outer and downward, towards above-mentioned food tray configuration;
Leak sensor, it is configured in above-mentioned food tray.
11. fuel cell systems according to claim 5, is characterized in that, this fuel cell system has the burner for above-mentioned reformer is heated,
Fuel using the eluting gas flowing out from above-mentioned venting hole as the burning use of said burner.
12. 1 kinds of fuel cell systems, is characterized in that, this fuel cell system comprises:
Pump, it is for delivery of liquid fuel;
Devulcanizer, it is configured in the downstream side of said pump, for removing desulfuration composition from aforesaid liquid fuel;
Kapillary, it is configured in the downstream side of above-mentioned devulcanizer, for the liquid fuel that utilizes above-mentioned devulcanizer to remove sulphur composition, passes through;
Reformer, it is configured in above-mentioned downstream side capillaceous, uses the liquid fuel that utilizes above-mentioned devulcanizer to remove sulphur composition to generate the reformed gas that contains hydrogen;
Fuel cell stack, the above-mentioned reformed gas that its use utilizes above-mentioned reformer to generate generates electricity.
13. fuel cell systems according to claim 12, is characterized in that,
Said pump is constant pressure pump.
14. fuel cell systems according to claim 12, is characterized in that,
Above-mentioned internal diameter capillaceous is 0.lmm～0.7mm.
15. fuel cell systems according to claim 12, is characterized in that,
Above-mentioned kapillary is wound into spirrillum.
CN201310279707.6A 2008-05-14 2009-05-14 Reforming system and fuel cell system Pending CN103588169A (en)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP2008-127362 2008-05-14
JP2008127362A JP5171384B2 (en) 2008-05-14 2008-05-14 Desulfurization apparatus and fuel cell system
JP2008149550A JP5226390B2 (en) 2008-06-06 2008-06-06 Fuel cell system and reforming system
JP2008-149550 2008-06-06
JP2008-159467 2008-06-18
JP2008159467A JP4918068B2 (en) 2008-06-18 2008-06-18 Fuel cell system
JP2008-179518 2008-07-09
JP2008179516A JP2010018467A (en) 2008-07-09 2008-07-09 Desulfurization apparatus and fuel cell system
JP2008179518A JP5373327B2 (en) 2008-07-09 2008-07-09 Desulfurization apparatus and fuel cell system
JP2008-179392 2008-07-09
JP2008-179516 2008-07-09
JP2008179392A JP5171443B2 (en) 2008-07-09 2008-07-09 Desulfurization apparatus and fuel cell system

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