TW201429037A - Desulfurizing device and fuel cell system - Google Patents

Desulfurizing device and fuel cell system Download PDF

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Publication number
TW201429037A
TW201429037A TW103114082A TW103114082A TW201429037A TW 201429037 A TW201429037 A TW 201429037A TW 103114082 A TW103114082 A TW 103114082A TW 103114082 A TW103114082 A TW 103114082A TW 201429037 A TW201429037 A TW 201429037A
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Taiwan
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liquid fuel
desulfurizer
gas
fuel
pressure
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TW103114082A
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Chinese (zh)
Inventor
Jun Akimoto
Takeshi Ibuka
Manabu Hiwatari
Hiroaki Watanabe
Tokuichi Ichikawa
Takayuki Hasegawa
Akiko Tamagawa
Takuo Nishiyama
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Nippon Oil 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 Nippon Oil Corp filed Critical Nippon Oil Corp
Publication of TW201429037A publication Critical patent/TW201429037A/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
    • H01M8/04—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
    • H01M8/06—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
    • H01M8/24—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 desulfurizing device and a fuel cell system. The desulfurizing device can prevent the gasification of the liquid fuel. The fuel cell system is provided with the desulfurizing device. In the desulfurizing device (3) of the fuel cell system, a control part (15) controls a heater (8), an inlet valve (9), a pump (11) and an outlet valve (12), so that the temperature measured by a thermometer (13), namely the temperature of the liquid fuel in a desulfurizer (7) is a preset temperature, namely the pressure measured by a pressure gauge (14), namely the pressure of the liquid fuel in the desulfurizer (7) is a preset pressure which is above a saturation vapor pressure of the liquid fuel under a preset temperature and is below the pressure resistance of the desulfurizer. Therefore the gasification of the liquid fuel can be prevented even the temperature of the liquid fuel in the desulfurizer (7) is increased.

Description

燃料電池系統及改質系統 Fuel cell system and upgrading system

本發明係涉及自液體燃料中除去硫成分之脫硫裝置、具有此種脫硫裝置之燃料電池系統及改質系統。 The present invention relates to a desulfurization apparatus for removing a sulfur component from a liquid fuel, a fuel cell system having such a desulfurization apparatus, and a upgrading system.

在燃料電池系統中，藉由改質器生成含有氫之改質氣體，並藉由燃料電池堆疊(stack)，使用該改質氣體來進行發電。於此種燃料電池系統中，在將作為改質原料之煤油等液體燃料供給至改質器中之情形時，為防止改質觸媒之劣化，需設置用於自液體燃料中除去硫成分之脫硫器。(例如，參照日本專利特開2004-323285號公報)。 In a fuel cell system, a reforming gas containing hydrogen is generated by a reformer, and the reformed gas is used to generate electricity by a fuel cell stack. In such a fuel cell system, when a liquid fuel such as kerosene as a reforming raw material is supplied to the reformer, in order to prevent deterioration of the reforming catalyst, it is necessary to provide a sulfur component for removing the sulfur component from the liquid fuel. Desulfurizer. (For example, refer to Japanese Laid-Open Patent Publication No. 2004-323285).

(本發明之第1側面) (The first aspect of the invention)

然而，在脫硫器中，為促進觸媒反應需加熱脫硫觸媒，但由於伴隨加熱脫硫觸媒之溫度上升，液體燃料會氣化，從而不僅難以進行高效率之脫硫，而且有可能會使脫硫觸媒劣化。 However, in the desulfurizer, in order to promote the catalyst reaction, it is necessary to heat the desulfurization catalyst, but since the temperature of the desulfurization catalyst is increased, the liquid fuel is vaporized, thereby making it difficult to perform high-efficiency desulfurization, and It may degrade the desulfurization catalyst.

因此，本發明之第1側面係有鑒於此種情況而研發者，目的在於提供一種可防止液體燃料氣化之脫硫裝置及具有此種脫硫裝置之燃料電池系統。 Therefore, the first aspect of the present invention has been made in view of such circumstances, and an object of the invention is to provide a desulfurization apparatus capable of preventing vaporization of liquid fuel and a fuel cell system having the same.

為達成上述目的，本發明之第1側面之脫硫裝置之特徵在於包括：脫硫器，其收容脫硫觸媒，該脫硫觸媒用於自供給至改質器中之液體燃料中除去硫成分，該改質器用於生成含有氫之改質氣體；加熱機構，其加熱脫硫觸媒；液體燃料導入機構，其將液體燃料導入至脫 硫器內；液體燃料導出機構，其將液體燃料自脫硫器內導出；溫度測量機構，其測量脫硫器內之液體燃料之溫度；壓力測量機構，其測量脫硫器內之液體燃料之壓力；以及控制機構，其對加熱機構、液體燃料導入機構及液體燃料導出機構進行控制，且，控制機構對加熱機構、液體燃料導入機構及液體燃料導出機構進行控制，使得由溫度測量機構測量之溫度達到特定溫度，由壓力測量機構測量之壓力達到特定溫度下之液體燃料之飽及蒸氣壓以上且為脫硫器之耐壓以下之特定壓力。 In order to achieve the above object, a first aspect of the present invention provides a desulfurization apparatus comprising: a desulfurizer for containing a desulfurization catalyst for removing from a liquid fuel supplied to a reformer; a sulfur component, the reformer is for generating a reformed gas containing hydrogen; a heating mechanism for heating the desulfurization catalyst; and a liquid fuel introduction mechanism for introducing the liquid fuel to the catalyst a sulfur fuel; a liquid fuel derivation mechanism that derives liquid fuel from the desulfurizer; a temperature measuring mechanism that measures the temperature of the liquid fuel in the desulfurizer; and a pressure measuring mechanism that measures the liquid fuel in the desulfurizer a pressure mechanism; and a control mechanism that controls the heating mechanism, the liquid fuel introduction mechanism, and the liquid fuel outlet mechanism, and the control mechanism controls the heating mechanism, the liquid fuel introduction mechanism, and the liquid fuel delivery mechanism to be measured by the temperature measuring mechanism The temperature reaches a certain temperature, and the pressure measured by the pressure measuring mechanism reaches a specific pressure above the saturated vapor pressure of the liquid fuel at a specific temperature and below the withstand voltage of the desulfurizer.

在該脫硫裝置中，藉由利用控制機構控制加熱機構、液體燃料導入機構及液體燃料導出機構，從而使由溫度測量機構測量之溫度、即脫硫器內之液體燃料之溫度達到例如可促進脫硫觸媒之觸媒反應之特定溫度。並且，使得由壓力測量機構測量之壓力、即脫硫器內之液體燃料之壓力達到特定溫度下之液體燃料之飽和蒸氣壓以上且為脫硫器之耐壓以下之特定壓力。因此，即使使脫硫器內之液體燃料之溫度上升，亦可防止液體燃料氣化。再者，所謂硫成分，係包括硫及硫化物之意。又，所謂脫硫器之耐壓，係指收容脫硫觸媒之容器可承受之內壓之最大值。 In the desulfurization apparatus, the temperature measured by the temperature measuring means, that is, the temperature of the liquid fuel in the desulfurizer can be promoted, for example, by controlling the heating means, the liquid fuel introducing means, and the liquid fuel discharging means by the control means. The specific temperature of the catalyst reaction of the desulfurization catalyst. Further, the pressure measured by the pressure measuring means, that is, the pressure of the liquid fuel in the desulfurizer is equal to or higher than the saturated vapor pressure of the liquid fuel at a specific temperature and below the pressure of the desulfurizer. Therefore, even if the temperature of the liquid fuel in the desulfurizer is raised, the liquid fuel can be prevented from vaporizing. Further, the so-called sulfur component means sulfur and sulfide. Moreover, the pressure resistance of the desulfurizer refers to the maximum internal pressure that the container containing the desulfurization catalyst can withstand.

在本發明之第1側面之脫硫裝置中，較好的是，控制機構在使由壓力測量機構測量之壓力上升之情形時，增加由液體燃料導入機構導入之液體燃料之導入量，並且減少由液體燃料導出機構導出之液體燃料之導出量；在使由壓力測量機構測量之壓力降低之情形時，減少由液體燃料導入機構導入之液體燃料之導入量，並且增加由液體燃料導出機構導出之液體燃料之導出量。根據該構成，可使由壓力測量機構測量之壓力、即脫硫器內之液體燃料之壓力迅速且確實地上升或降低。 In the desulfurization apparatus according to the first aspect of the present invention, it is preferable that the control means increases the introduction amount of the liquid fuel introduced by the liquid fuel introduction means when the pressure measured by the pressure measuring means is increased, and reduces The amount of liquid fuel derived from the liquid fuel delivery mechanism; when the pressure measured by the pressure measuring mechanism is lowered, the introduction amount of the liquid fuel introduced by the liquid fuel introduction mechanism is reduced, and the amount derived by the liquid fuel delivery mechanism is increased. The amount of liquid fuel exported. According to this configuration, the pressure measured by the pressure measuring means, that is, the pressure of the liquid fuel in the desulfurizer can be quickly and surely increased or decreased.

又，本發明之第1側面之燃料電池系統包括：上述脫硫裝置；改 質器，其使用藉由脫硫裝置除去了硫成分之液體燃料生成含有氫之改質氣體；以及燃料電池堆疊，其使用藉由改質器生成之改質氣體進行發電。 Further, the fuel cell system according to the first aspect of the present invention includes: the above-described desulfurization device; A massifier that uses a liquid fuel from which a sulfur component is removed by a desulfurization device to generate a reformed gas containing hydrogen; and a fuel cell stack that uses a reformed gas generated by a reformer to generate electricity.

根據該燃料電池系統，因具有上述脫硫裝置，所以即使使脫硫器內之液體燃料之溫度上升，亦可防止液體燃料氣化。 According to the fuel cell system, since the desulfurization device is provided, the liquid fuel can be prevented from vaporizing even if the temperature of the liquid fuel in the desulfurizer is increased.

根據本發明之第1側面，可防止液體燃料之氣化。 According to the first aspect of the invention, vaporization of the liquid fuel can be prevented.

(本發明之第2側面) (The second aspect of the invention)

在燃料電池系統中，藉由改質器生成含有氫之改質氣體，並藉由燃料電池堆疊，使用該改質氣體來進行發電。在此種燃料電池系統中，於將作為改質原料之煤油等液體燃料供給至改質器中之情形時，為防止改質觸媒之劣化，需設置用於自液體燃料中除去硫成分之脫硫器。(例如，參照日本專利特開2004-323285號公報)。 In a fuel cell system, a reforming gas containing hydrogen is generated by a reformer, and the reformed gas is used to generate electricity by stacking the fuel cells. In such a fuel cell system, when a liquid fuel such as kerosene as a reforming raw material is supplied to the reformer, in order to prevent deterioration of the reforming catalyst, it is necessary to provide a sulfur component for removing the sulfur component from the liquid fuel. Desulfurizer. (For example, refer to Japanese Laid-Open Patent Publication No. 2004-323285).

然而，在脫硫器中，為促進觸媒反應而需加熱脫硫觸媒，但使脫硫觸媒自常溫上升至特定之脫硫溫度(例如200℃)需要相當長之時間。因此，存在一旦停止時直至再啟動為止需耗費時間之問題。 However, in the desulfurizer, it is necessary to heat the desulfurization catalyst in order to promote the catalyst reaction, but it takes a relatively long time for the desulfurization catalyst to rise from the normal temperature to a specific desulfurization temperature (for example, 200 ° C). Therefore, there is a problem that it takes time to stop until it is restarted.

因此，本發明之第2側面係有鑒於此種情況而研發者，目的在於提供一種可謀求縮短直至再啟動為止之時間之脫硫裝置以及具有此種脫硫裝置之燃料電池系統。 Therefore, the second aspect of the present invention has been made in view of such circumstances, and an object of the invention is to provide a desulfurization apparatus capable of shortening the time until restarting, and a fuel cell system having such a desulfurization apparatus.

為達成上述目的，本發明之第2側面之脫硫裝置之特徵在於包括：脫硫器，其收容脫硫觸媒，該脫硫觸媒自供給至改質器中之液體燃料中除去硫成分，該改質器用於生成含有氫之改質氣體；加熱機構，其加熱脫硫觸媒；液體燃料導入機構，其將液體燃料導入至脫硫器內；液體燃料導出機構，其將液體燃料自脫硫器內導出；溫度測量機構，其測量脫硫器內之液體燃料之溫度；控制機構，其控制加熱機構、液體燃料導入機構及液體燃料導出機構，且，控制機構對液體燃料導入機構及液體燃料導出機構之至少一個進行控制，使得在輸入有 暫停信號之情形時，停止自脫硫器內供給液體燃料，並且對加熱機構進行控制，使得由測量機構測量之溫度達到比常溫高且比通常運轉時之溫度低之特定溫度。 In order to achieve the above object, a desulfurization apparatus according to a second aspect of the present invention includes a desulfurizer that houses a desulfurization catalyst that removes sulfur components from a liquid fuel supplied to the reformer. The reformer is for generating a reformed gas containing hydrogen; a heating mechanism for heating the desulfurization catalyst; a liquid fuel introduction mechanism for introducing the liquid fuel into the desulfurizer; and a liquid fuel discharge mechanism for the liquid fuel a desulfurizer; a temperature measuring mechanism that measures the temperature of the liquid fuel in the desulfurizer; a control mechanism that controls the heating mechanism, the liquid fuel introduction mechanism, and the liquid fuel deriving mechanism, and the control mechanism controls the liquid fuel and the liquid fuel introduction mechanism At least one of the liquid fuel delivery mechanisms is controlled such that there is In the case of a pause signal, the supply of liquid fuel from the desulfurizer is stopped, and the heating mechanism is controlled such that the temperature measured by the measuring mechanism reaches a specific temperature higher than normal temperature and lower than the temperature during normal operation.

在該脫硫裝置中，在輸入有暫停信號之情形時，藉由利用控制機構控制液體燃料導入機構及液體燃料導出機構之至少一個，而停止自脫硫器內供給液體燃料。此時，藉由利用控制機構控制加熱機構，而將由溫度測量機構測量之溫度、即脫硫器內之液體燃料之溫度維持為比常溫高且為通常運轉時之溫度以下之特定溫度。藉由，與使脫硫裝置停止而使溫度降低至常溫之情形相比，由於直至加熱至通常運轉時之溫度、即特定之脫硫溫度為止之時間被縮短，因此可謀求縮短直至再啟動為止之時間。再者，所謂硫成分，係包括硫及硫化物之意。 In the desulfurization apparatus, when a pause signal is input, at least one of the liquid fuel introduction mechanism and the liquid fuel discharge mechanism is controlled by the control means to stop the supply of the liquid fuel from the desulfurizer. At this time, by controlling the heating means by the control means, the temperature measured by the temperature measuring means, that is, the temperature of the liquid fuel in the desulfurizer is maintained at a specific temperature higher than the normal temperature and lower than the temperature at the time of normal operation. By shortening the time until the temperature at the normal operation, that is, the specific desulfurization temperature, is shortened compared with the case where the temperature is lowered to the normal temperature by stopping the desulfurization apparatus, the shortening can be shortened until restarting. Time. Further, the so-called sulfur component means sulfur and sulfide.

在本發明之第2側面之脫硫裝置中，較好的是更包括：儲存容器，其將由液體燃料導出機構導出之液體燃料暫時儲存；以及儲存量測量機構，其測量儲存在儲存容器中之液體燃料之儲存量，且，儲存量測量機構在儲存量達到特定儲存量之情形時，將暫停信號輸出至控制機構中。根據該構成，藉由將液體燃料暫時儲存在儲存容器中，可使液體燃料向改質器等中之供給穩定化。又，在儲存容器內之儲存量達到特定儲存量之情形時，儲存量測量機構將暫停信號輸出至控制機構中，因此可防止例如由儲存量超量所引起之儲存容器之破損等。 In the desulfurization apparatus of the second aspect of the present invention, it is preferable to further include: a storage container that temporarily stores the liquid fuel derived from the liquid fuel delivery mechanism; and a storage amount measuring mechanism that measures the storage in the storage container The storage amount of the liquid fuel, and the storage amount measuring mechanism outputs the pause signal to the control mechanism when the storage amount reaches a certain storage amount. According to this configuration, by temporarily storing the liquid fuel in the storage container, the supply of the liquid fuel to the reformer or the like can be stabilized. Further, when the storage amount in the storage container reaches a certain storage amount, the storage amount measuring means outputs a pause signal to the control means, so that damage of the storage container caused by, for example, an excessive amount of storage can be prevented.

又，本發明之第2側面之燃料電池系統包括：上述脫硫裝置；改質器，其使用藉由脫硫裝置除去了硫成分之液體燃料生成含有氫之改質氣體；以及燃料電池堆疊，其使用藉由改質器生成之改質氣體進行發電。 Further, a fuel cell system according to a second aspect of the present invention includes: the above-described desulfurization device; a reformer that uses a liquid fuel from which a sulfur component is removed by a desulfurization device to generate a reformed gas containing hydrogen; and a fuel cell stack, It uses the reformed gas generated by the reformer to generate electricity.

根據該燃料電池系統，因具有上述脫硫裝置，因此能謀求縮短至再啟動為止之時間。 According to this fuel cell system, since the above-described desulfurization device is provided, it is possible to shorten the time until restarting.

根據本發明之第2側面，可謀求縮短至再啟動為止之時間。 According to the second aspect of the present invention, it is possible to shorten the time until restarting.

(本發明之第3側面) (The third aspect of the invention)

在燃料電池系統中，利用改質器生成含有氫之改質氣體，並藉由燃料電池堆疊，使用該改質氣體進行發電。在此種燃料電池系統中，於將作為改質原料之煤油等液體燃料供給至改質器中之情形時，為防止改質觸媒之劣化，需設置用於自液體燃料中除去硫成分之脫硫器。(例如，參照日本專利特開2004-323285號公報)。 In a fuel cell system, a reforming gas containing hydrogen is generated by a reformer, and the reformed gas is used to generate electricity by stacking the fuel cells. In such a fuel cell system, when a liquid fuel such as kerosene as a reforming raw material is supplied to the reformer, in order to prevent deterioration of the reforming catalyst, it is necessary to provide a sulfur component for removing the sulfur component from the liquid fuel. Desulfurizer. (For example, refer to Japanese Laid-Open Patent Publication No. 2004-323285).

然而，在脫硫器內中，隨著液體燃料之溫度之降低，壓力會降低。例如，在停止運轉時，壓力比通常運轉時降低約20%左右。此時，有可能會導致液體燃料氣化，使脫硫觸媒劣化。又，當脫硫器內之壓力成為負壓時，亦可能會產生脫硫器之破損、重新開始運轉時空氣混入脫硫器中等之問題。 However, in the desulfurizer, as the temperature of the liquid fuel decreases, the pressure decreases. For example, when the operation is stopped, the pressure is reduced by about 20% compared with the normal operation. At this time, there is a possibility that the liquid fuel is vaporized and the desulfurization catalyst is deteriorated. Further, when the pressure in the desulfurizer becomes a negative pressure, there is a possibility that the desulfurizer is broken and the air is mixed into the desulfurizer at the time of restarting the operation.

因此，本發明之第3側面係有鑒於此種情況而研發者，目的在於提供一種可防止因壓力降低而對脫硫器帶來不良影響之脫硫裝置以及具有此種脫硫裝置之燃料電池系統。 Therefore, the third aspect of the present invention has been made in view of such circumstances, and an object thereof is to provide a desulfurization apparatus capable of preventing adverse effects on a desulfurizer due to pressure drop, and a fuel cell having such a desulfurization apparatus. system.

為達成上述目的，本發明之第3側面之脫硫裝置之特徵在於包括：脫硫器，其收容脫硫觸媒，該脫硫觸媒自供給至改質器中之液體燃料中除去硫成分，該改質器用於生成含有氫之改質氣體；液體燃料導入機構，其將液體燃料導入至脫硫器內；液體燃料導出機構，其將液體燃料自脫硫器內導出；溫度測量機構，其測量脫硫器內之液體燃料之溫度；壓力測量機構，其測量脫硫器內之液體燃料之壓力；以及控制機構，其控制液體燃料導入機構及液體燃料導出機構，且，控制機構對液體燃料導入機構及液體燃料導出機構進行控制，使得在由溫度測量機構測量之溫度成為比通常運轉時之溫度低之特定溫度以下之情形時，由壓力測量機構測量之壓力達到作為正壓之特定壓力。 In order to achieve the above object, a third aspect of the present invention provides a desulfurization apparatus comprising: a desulfurizer for containing a desulfurization catalyst, wherein the desulfurization catalyst removes sulfur component from a liquid fuel supplied to the reformer The reformer is for generating a reformed gas containing hydrogen; a liquid fuel introduction mechanism for introducing the liquid fuel into the desulfurizer; a liquid fuel discharge mechanism for discharging the liquid fuel from the desulfurizer; and a temperature measuring mechanism, Measuring the temperature of the liquid fuel in the desulfurizer; a pressure measuring mechanism that measures the pressure of the liquid fuel in the desulfurizer; and a control mechanism that controls the liquid fuel introduction mechanism and the liquid fuel outlet mechanism, and the control mechanism is directed to the liquid The fuel introduction mechanism and the liquid fuel outlet mechanism are controlled such that when the temperature measured by the temperature measuring mechanism becomes lower than a specific temperature lower than the temperature during normal operation, the pressure measured by the pressure measuring mechanism reaches a specific pressure as a positive pressure .

在該脫硫裝置中，在由溫度測量機構測量之溫度、即脫硫器內之液體燃料之溫度成為比通常運轉時之溫度(例如200℃)低之特定溫度 (例如100℃)以下之情形時，藉由利用控制機構控制液體燃料導入機構及液體燃料導出機構，使由壓力測量機構測量之壓力達到作為正壓(負壓以上)之特定壓力。因此，例如在停止運轉時，即使隨著液體燃料之溫度之降低而壓力降低，由於作為正壓之特定壓力被保持，所以亦可防止因壓力降低引起之例如液體燃料氣化、脫硫器之破損等之對脫硫器之不良影響。再者，所謂硫成分係包括硫及硫化物之意。 In the desulfurization apparatus, the temperature measured by the temperature measuring means, that is, the temperature of the liquid fuel in the desulfurizer becomes a specific temperature lower than the temperature (for example, 200 ° C) during normal operation. In the case of (for example, 100 ° C) or less, the pressure measured by the pressure measuring means is brought to a specific pressure as a positive pressure (negative pressure or more) by controlling the liquid fuel introduction means and the liquid fuel discharge means by the control means. Therefore, for example, when the operation is stopped, even if the pressure is lowered as the temperature of the liquid fuel is lowered, since the specific pressure as the positive pressure is maintained, it is possible to prevent, for example, the vaporization of the liquid fuel due to the pressure drop, and the desulfurizer. The adverse effects of damage, etc. on the desulfurizer. Further, the so-called sulfur component means sulfur and sulfide.

在本發明之第3側面之脫硫裝置中，較好的是，控制機構在使由壓力測量機構測量之壓力上升之情形時，增加由液體燃料導入機構導入之液體燃料之導入量，並且減少由液體燃料導出機構導出之液體燃料之導出量；在使由壓力測量機構測量之壓力降低之情形時，減少由液體燃料導入機構導入之液體燃料之導入量，並且增加由液體燃料導出機構導出之液體燃料之之導出量。根據該構成，可迅速且確實地使由壓力測量機構測量之壓力、即脫硫器內之液體燃料之壓力上升或降低。 In the desulfurization apparatus according to the third aspect of the present invention, preferably, the control means increases the introduction amount of the liquid fuel introduced by the liquid fuel introduction means when the pressure measured by the pressure measuring means is increased, and reduces The amount of liquid fuel derived from the liquid fuel delivery mechanism; when the pressure measured by the pressure measuring mechanism is lowered, the introduction amount of the liquid fuel introduced by the liquid fuel introduction mechanism is reduced, and the amount derived by the liquid fuel delivery mechanism is increased. The derived amount of liquid fuel. According to this configuration, the pressure measured by the pressure measuring means, that is, the pressure of the liquid fuel in the desulfurizer can be quickly and surely increased or decreased.

又，本發明之第3側面之燃料電池系統包括：上述脫硫裝置；改質器，其使用藉由脫硫裝置除去了硫成分之液體燃料生成含有氫之改質氣體；以及燃料電池堆疊，其使用藉由改質器生成之改質氣體進行發電。 Further, a fuel cell system according to a third aspect of the present invention includes: the above-described desulfurization device; a reformer that uses a liquid fuel from which a sulfur component is removed by a desulfurization device to generate a reformed gas containing hydrogen; and a fuel cell stack, It uses the reformed gas generated by the reformer to generate electricity.

根據該燃料電池系統，因具有上述脫硫裝置，因此即使壓力隨著液體燃料之溫度之降低而降低，亦可防止因壓力降低對脫硫器造成之不良影響。 According to this fuel cell system, since the above-described desulfurization device is provided, even if the pressure is lowered as the temperature of the liquid fuel is lowered, the adverse effect on the desulfurizer due to the pressure drop can be prevented.

根據本發明之第3側面，可防止因壓力降低對脫硫器造成之不良影響。 According to the third aspect of the present invention, it is possible to prevent the adverse effect on the desulfurizer caused by the pressure drop.

(本發明之第4側面) (Fourth aspect of the invention)

在燃料電池系統中，利用改質器生成含有氫之改質氣體，並藉由燃料電池堆疊，使用該改質氣體進行發電。在此種燃料電池系統中， 於將作為改質原料之煤油等液體燃料供給至改質器中之情形時，為防止改質觸媒之劣化，需設置用於自液體燃料中除去硫成分之脫硫器。(例如，參照日本專利特開2004-323285號公報)。 In a fuel cell system, a reforming gas containing hydrogen is generated by a reformer, and the reformed gas is used to generate electricity by stacking the fuel cells. In such a fuel cell system, In the case where liquid fuel such as kerosene as a reforming raw material is supplied to the reformer, in order to prevent deterioration of the reforming catalyst, a desulfurizer for removing sulfur components from the liquid fuel is required. (For example, refer to Japanese Laid-Open Patent Publication No. 2004-323285).

然而，由於沼氣及氫氣等氣體與液體燃料一起自脫硫器排出，因此有可能阻礙對改質器定量供給液體燃料等，對脫硫器之後段帶來不良影響。 However, since gas such as biogas and hydrogen gas is discharged from the desulfurizer together with the liquid fuel, there is a possibility that the quantitative supply of the liquid fuel to the reformer may be hindered, which may adversely affect the subsequent stage of the desulfurizer.

因此，本發明之第4側面係有鑒於此種情況而研發者，目的在於提供一種可防止對後段之不良影響且可自液體燃料中確實地除去硫成分之脫硫裝置以及具有此種脫硫裝置之燃料電池系統。 Accordingly, the fourth aspect of the present invention has been made in view of such circumstances, and an object thereof is to provide a desulfurization apparatus capable of preventing a bad influence on a rear stage and capable of reliably removing a sulfur component from a liquid fuel, and having such a desulfurization The fuel cell system of the device.

為達成上述目的，本發明之第4側面之脫硫裝置之特徵在於包括：脫硫器，其自供給至改質器中之液體燃料中除去硫成分，該改質器用於生成含有氫之改質氣體；氣液分離容器，其儲存自脫硫器排出之液體燃料及氣體；液體燃料排出管線，其用於自氣液分離容器排出液體燃料；氣體排出管線，其用於自氣液分離容器排出氣體；開閉閥，其設在氣體排出管線上，用於開啟及關閉氣體之流通；以及節流機構(抑制在氣體之流通被開啟時之脫硫器內之壓力降低之節流機構)，其在開閉閥之下游側設在氣體排出管線上，用於阻礙氣體之流通。 In order to achieve the above object, the fourth aspect of the present invention provides a desulfurization apparatus comprising: a desulfurizer for removing a sulfur component from a liquid fuel supplied to a reformer, wherein the reformer is for generating a hydrogen-containing reform a gas-liquid separation vessel for storing liquid fuel and gas discharged from a desulfurizer; a liquid fuel discharge line for discharging liquid fuel from the gas-liquid separation vessel; and a gas discharge line for separating the vessel from the gas-liquid separation Exhaust gas; an on-off valve disposed on the gas discharge line for opening and closing the flow of the gas; and a throttling mechanism (throttle mechanism for suppressing a decrease in pressure in the desulfurizer when the gas flow is turned on), It is disposed on the downstream side of the opening and closing valve on the gas discharge line for blocking the circulation of the gas.

在該脫硫裝置中，與液體燃料一起自脫硫器被排出之氣體在氣液分離容器中與液體燃料分離，經由氣體排出管線自氣液分離容器被排出。因此，可防止混入了氣體之液體燃料被供給至脫硫裝置之後段。並且，在氣體排出管線上，在開啟及關閉氣體流通之開閉閥之下游側設有阻礙氣體流通之節流機構。因此，即使為將氣體經由氣體排出管線自氣液分離容器排出而利用開閉閥開啟氣體之流通，脫硫器內之壓力之降低亦會被節流機構抑制。因此，根據該脫硫裝置，可防止對後段之不良影響且可自液體燃料中確實地除去硫成分。再者，所謂硫成 分係包括硫及硫化物之意。 In the desulfurization apparatus, the gas discharged from the desulfurizer together with the liquid fuel is separated from the liquid fuel in the gas-liquid separation container, and is discharged from the gas-liquid separation container via the gas discharge line. Therefore, it is possible to prevent the liquid fuel in which the gas is mixed from being supplied to the subsequent stage of the desulfurization apparatus. Further, in the gas discharge line, a throttle mechanism that blocks the flow of the gas is provided on the downstream side of the opening and closing valve that opens and closes the gas flow. Therefore, even if the gas is discharged from the gas-liquid separation container through the gas discharge line and the gas is opened by the opening and closing valve, the pressure drop in the desulfurizer is also suppressed by the throttle mechanism. Therefore, according to the desulfurization apparatus, it is possible to prevent adverse effects on the rear stage and to reliably remove the sulfur component from the liquid fuel. Furthermore, the so-called sulfur The division includes the meaning of sulfur and sulfide.

在本發明之第4側面之脫硫裝置中，較好的是，在開閉閥關閉氣體之流通之情形時，當氣液分離容器內之氣體之量超過特定量時，開閉閥分多次開啟氣體之流通。根據該構成，可更確實地抑制為將氣體經由氣體排出管線自氣液分離容器排出而由開閉閥開啟氣體之流通時之脫硫器內之壓力降低。 In the desulfurization apparatus according to the fourth aspect of the present invention, preferably, when the opening and closing valve closes the flow of the gas, when the amount of the gas in the gas-liquid separation container exceeds a certain amount, the opening and closing valve is opened several times. The circulation of gas. According to this configuration, it is possible to more reliably suppress a pressure drop in the desulfurizer when the gas is discharged from the gas-liquid separation container through the gas discharge line and the gas is opened by the opening and closing valve.

在本發明之第4側面之脫硫裝置中，較好的是，氣體排出管線與對改質器之改質觸媒進行加熱之燃燒器相連接。根據該構成，可有效地利用與液體燃料一起自脫硫器被排出之氣體作為燃燒器之燃料。 In the desulfurization apparatus according to the fourth aspect of the present invention, preferably, the gas discharge line is connected to a burner that heats the reforming catalyst of the reformer. According to this configuration, the gas discharged from the desulfurizer together with the liquid fuel can be effectively utilized as the fuel of the burner.

又，本發明之第4側面之燃料電池系統包括：上述脫硫裝置；改質器，其使用藉由脫硫裝置除去了硫成分之液體燃料生成含有氫之改質氣體；以及燃料電池堆疊，其使用藉由改質器生成之改質氣體進行發電。 Further, a fuel cell system according to a fourth aspect of the present invention includes: the above-described desulfurization device; a reformer that uses a liquid fuel from which a sulfur component is removed by a desulfurization device to generate a reformed gas containing hydrogen; and a fuel cell stack, It uses the reformed gas generated by the reformer to generate electricity.

根據該燃料電池系統，因具有上述脫硫裝置，因此可防止對脫硫裝置之後段之不良影響且可自液體燃料中確實地除去硫成分。 According to this fuel cell system, since the above-described desulfurization apparatus is provided, it is possible to prevent adverse effects on the subsequent stage of the desulfurization apparatus and to reliably remove sulfur components from the liquid fuel.

根據本發明之第4側面，可防止對脫硫裝置之後段不良影響，且能自液體燃料中確實地除去硫成分。 According to the fourth aspect of the present invention, it is possible to prevent adverse effects on the subsequent stage of the desulfurization apparatus, and it is possible to reliably remove the sulfur component from the liquid fuel.

(本發明之第5側面) (The fifth aspect of the invention)

在燃料電池系統中，對液體燃料等進行改質而製造包含氫之改質氣體，使該改質氣體及包含氧之氣體發生反應而發電。於將使用煤油等包含硫成分之燃料作為投入至燃料電池系統中之原燃料之情形時，改質觸媒由於接觸原燃料中之硫成分，因此會發生硫中毒而使改質性能劣化。因此，作為燃料電池系統，有在改質反應之前自原燃料中除去硫成分者。(例如，參照日本專利特開2004-213941號公報)。 In a fuel cell system, a liquid fuel or the like is modified to produce a reformed gas containing hydrogen, and the reformed gas and a gas containing oxygen are reacted to generate electricity. When a fuel containing a sulfur component such as kerosene is used as a raw fuel to be supplied to a fuel cell system, since the modified catalyst contacts the sulfur component in the raw fuel, sulfur poisoning occurs to deteriorate the reform performance. Therefore, as a fuel cell system, there is a case where a sulfur component is removed from a raw fuel before a reforming reaction. (For example, refer to Japanese Laid-Open Patent Publication No. 2004-213941).

然而，在包含於原燃料中之硫濃度比較高之情形時，為充分除去硫成分，考慮使脫硫器內之壓力達到比大氣壓高之壓力來促進脫硫反 應。然而，在使脫硫器內達到高壓之情形時，高壓之液體燃料會自該脫硫器流入至後段之改質器內。於此情形時，將難以控制高壓之液體燃料之流量，改質性能會降低，而作為燃料電池系統之性能會降低。又，在使脫硫器內達到高壓時，後段之配管、反應容器、泵等設備會產生耐久性之問題，該等設備需要與高壓相適應，從而導致成本提高。 However, in the case where the concentration of sulfur contained in the raw fuel is relatively high, in order to sufficiently remove the sulfur component, it is considered that the pressure in the desulfurizer reaches a pressure higher than atmospheric pressure to promote the desulfurization reaction. should. However, when the high pressure is reached in the desulfurizer, the high pressure liquid fuel flows from the desulfurizer to the reformer in the latter stage. In this case, it is difficult to control the flow rate of the high-pressure liquid fuel, the deterioration performance is lowered, and the performance as a fuel cell system is lowered. Further, when the high pressure is reached in the desulfurizer, the piping, the reaction vessel, the pump, and the like in the latter stage have a problem of durability, and the equipment needs to be adapted to the high pressure, resulting in an increase in cost.

因此，本發明之第5側面之目的在於提供一種即使在高壓下進行脫硫之情形時，亦可提高脫硫器之後段之設備之耐久性、實現低成本且防止性能降低之燃料電池系統。 Therefore, an object of the fifth aspect of the present invention is to provide a fuel cell system which can improve the durability of the apparatus in the subsequent stage of the desulfurizer, realize low cost, and prevent performance degradation even when desulfurization is performed under high pressure.

本發明之第5側面之燃料電池系統之特徵在於包括：脫硫器，其在比大氣壓高之壓力下自液體之原燃料中除去硫成分而生成液體燃料；儲油槽，其設有與朝大氣開放之排氣孔，用於儲存自脫硫器排出之液體燃料；輸出泵，其將液體燃料自儲油槽內送出；改質器，其配置在輸出泵之下游側，對液體燃料進行改質而生成改質氣體；以及燃料電池堆疊，其使用改質氣體進行發電。 A fuel cell system according to a fifth aspect of the present invention, comprising: a desulfurizer that removes a sulfur component from a raw fuel of a liquid at a pressure higher than atmospheric pressure to generate a liquid fuel; and an oil storage tank provided with an atmosphere An open venting hole for storing liquid fuel discharged from the desulfurizer; an output pump for discharging liquid fuel from the oil storage tank; and a reformer disposed on a downstream side of the output pump for modifying the liquid fuel And generating a reformed gas; and a fuel cell stack that uses the reformed gas to generate electricity.

在本發明之第5側面之燃料電池系統中，儲存液體燃料之儲油槽係配置於在高壓下進行脫硫反應之脫硫器及改質器之間，在該儲油槽上設有與朝大氣開放之排放孔。因此，當在脫硫器內經脫硫之高壓之液體燃料流入至儲油槽內時，包含於液體燃料中之氣體與液體燃料分離而藉由排放孔自儲油槽內排出。由於包含於液體燃料中之氣體被排出，因此在儲油槽之下游側，可增加液體燃料之流量控制之可靠性。因此，可確實地控制流入至改質器內之液體燃料之流量，防止改質性能之降低。又，由於高壓狀態之液體燃料不流入至儲油槽之下游側，因此無需與高壓相適應之設備，可提高儲油槽之後段設備之耐久性，從而可實現低成本。 In the fuel cell system according to the fifth aspect of the present invention, the oil storage tank for storing the liquid fuel is disposed between the desulfurizer and the reformer that performs the desulfurization reaction under high pressure, and is disposed on the oil storage tank and facing the atmosphere. Open drain hole. Therefore, when the desulfurized high-pressure liquid fuel in the desulfurizer flows into the oil storage tank, the gas contained in the liquid fuel is separated from the liquid fuel and discharged from the oil storage tank through the discharge hole. Since the gas contained in the liquid fuel is discharged, the reliability of the flow control of the liquid fuel can be increased on the downstream side of the oil reservoir. Therefore, the flow rate of the liquid fuel flowing into the reformer can be surely controlled to prevent the deterioration of the reform performance. Further, since the liquid fuel in the high pressure state does not flow into the downstream side of the oil storage tank, the equipment suitable for the high pressure is not required, and the durability of the equipment in the subsequent stage of the oil storage tank can be improved, thereby achieving low cost.

在本發明之第5側面之燃料電池系統中，較好的是包括：恆壓 泵，其以恆壓將原燃料加壓輸送入脫硫器內；以及毛細管，其配置在脫硫器之下游側且配置在儲油槽之上游側。 In the fuel cell system of the fifth aspect of the invention, it is preferable to include: constant pressure a pump that pressurizes the raw fuel into the desulfurizer at a constant pressure; and a capillary tube disposed on a downstream side of the desulfurizer and disposed on an upstream side of the oil storage tank.

於此情形時，原燃料以恆壓流入脫硫器內，自脫硫器之流出量受到節流。因此，不使用高價之泵，便可使脫硫器內之壓力高於大氣壓，並且可將原燃料(液體燃料)之流量保持為較低。一般亦可考慮利用節流孔、針型閥等來替代毛細管。然而，延長節流孔部分之流路存在極限，因此為減小自脫硫器被排出之高壓之液體燃料之流量，必需使節流孔部分之直徑極小。此處，在脫硫器中係藉由脫硫觸媒進行液體燃料之脫硫，但有時脫硫觸媒會包含在藉由脫硫器除去了硫成分之液體燃料中。因此，在利用節流孔、針型閥等之情形時，自脫硫器流出之脫硫觸媒有時會堵塞節流孔部分之流路。相對於此，在本發明之燃料電池系統中，如上所述般使用了毛細管，因此可根據毛細管之長度而在一定程度上增大毛細管之內徑。因此，極難發生由脫硫觸媒引起之堵塞之情形。 In this case, the raw fuel flows into the desulfurizer at a constant pressure, and the outflow amount from the desulfurizer is throttled. Therefore, without using a high-priced pump, the pressure in the desulfurizer can be higher than atmospheric pressure, and the flow rate of the raw fuel (liquid fuel) can be kept low. It is also generally conceivable to use an orifice, a needle valve or the like instead of a capillary. However, there is a limit to extending the flow path of the orifice portion, and therefore, in order to reduce the flow rate of the high-pressure liquid fuel discharged from the desulfurizer, it is necessary to make the diameter of the orifice portion extremely small. Here, in the desulfurizer, the desulfurization catalyst is used for desulfurization of the liquid fuel, but sometimes the desulfurization catalyst is contained in the liquid fuel from which the sulfur component is removed by the desulfurizer. Therefore, in the case of using an orifice, a needle valve, or the like, the desulfurization catalyst flowing out of the desulfurizer sometimes blocks the flow path of the orifice portion. On the other hand, in the fuel cell system of the present invention, since the capillary is used as described above, the inner diameter of the capillary can be increased to some extent depending on the length of the capillary. Therefore, it is extremely difficult to cause clogging caused by the desulfurization catalyst.

在本發明之第5側面之燃料電池系統中，較好的是包括：氣液分離容器，其用於將自脫硫器排出之液體燃料及氣體分離；液體燃料排出管線，其用於自氣液分離容器排出液體燃料；氣體排出管線，其用於自氣液分離容器排出氣體；開閉閥，其設置在氣體排出管線上，用於開啟及關閉氣體之流通；節流機構，其設置在氣體排出管線之開閉閥之下游側，用於阻礙氣體流通；以及流量計，其設置在液體燃料排出管線上，且，毛細管係設置在液體燃料排出管線中之流量計之上游側，儲油槽在液體燃料排出管線上之流量計之下游側與液體燃料排出管線相連結。 In the fuel cell system of the fifth aspect of the present invention, preferably, the present invention comprises: a gas-liquid separation vessel for separating liquid fuel and gas discharged from the desulfurizer; and a liquid fuel discharge line for self-gasification The liquid separation container discharges the liquid fuel; the gas discharge line is used for discharging the gas from the gas-liquid separation container; the opening and closing valve is disposed on the gas discharge line for opening and closing the circulation of the gas; and the throttle mechanism is disposed in the gas a downstream side of the opening and closing valve of the discharge line for obstructing gas circulation; and a flow meter disposed on the liquid fuel discharge line, and the capillary system is disposed on the upstream side of the flow meter in the liquid fuel discharge line, and the oil storage tank is in the liquid The downstream side of the flow meter on the fuel discharge line is coupled to the liquid fuel discharge line.

於此情形時，與液體燃料一起自脫硫器被排出之氣體在氣液分離容器與液體燃料分離，經由氣體排出管線自氣液分離容器被排出。在氣體排出管線上，在開啟及關閉氣體之流通之開閉閥之下游側設有阻 礙氣體流通之節流機構。因此，即使為將氣體經由氣體排出管線自氣液分離容器排出而由開閉閥開啟氣體之流通，脫硫器內之壓力之降低亦會被節流機構抑制。因此，藉由將脫硫器內之壓力保持在高壓，可確實地自原燃料中除去硫成分。另一方面，液體燃料經由液體燃料排出管線流入至儲油槽內。由於在液體燃料排出管線上設有流量計，因此可穩定地測量與氣體分離後之液體燃料之流量。 In this case, the gas discharged from the desulfurizer together with the liquid fuel is separated from the liquid fuel in the gas-liquid separation container, and is discharged from the gas-liquid separation container via the gas discharge line. On the gas discharge line, a resistance is provided on the downstream side of the opening and closing valve for opening and closing the gas flow. A throttling mechanism that hinders gas circulation. Therefore, even if the gas is discharged from the gas-liquid separation container through the gas discharge line and the gas is opened by the opening and closing valve, the pressure drop in the desulfurizer is also suppressed by the throttle mechanism. Therefore, by maintaining the pressure in the desulfurizer at a high pressure, the sulfur component can be surely removed from the raw fuel. On the other hand, the liquid fuel flows into the sump via the liquid fuel discharge line. Since the flow meter is provided on the liquid fuel discharge line, the flow rate of the liquid fuel separated from the gas can be stably measured.

在本發明之第5側面之燃料電池系統中，較好的是包括：水位感測器，其測量儲油槽內之液體燃料之低水位及高水位；計時器，其測量水位感測器自檢測到低水位至檢測到高水位為止之時間；以及計算機構，其根據計時器之測量時間，算出液體燃料之流量。 In the fuel cell system of the fifth aspect of the present invention, preferably, the water level sensor includes: a water level sensor for measuring a low water level and a high water level of the liquid fuel in the oil storage tank; and a timer for measuring the water level sensor self-detection The time from the low water level to the detection of the high water level; and the calculation mechanism that calculates the flow rate of the liquid fuel based on the measurement time of the timer.

於此情形時，藉由計時器測量水位感測器自檢測到低水位至檢測到高水位為止之時間，計算機構根據計時器之測量時間算出液體燃料之流量，因此無需另外設置流量計。由此，可謀求更低成本化。 In this case, the time period from the detection of the low water level to the detection of the high water level by the water level sensor is measured by the timer, and the calculation mechanism calculates the flow rate of the liquid fuel based on the measurement time of the timer, so there is no need to separately set the flow meter. Thereby, it is possible to achieve lower cost.

在本發明之第5側面之燃料電池系統中，較好的是，儲油槽之下部起到觸媒片儲存部之作用，其用於蓄積與液體燃料一起自脫硫器流入之脫硫觸媒片，儲油槽內之液體燃料之流入口及流出口位於觸媒片儲存部之上方。 In the fuel cell system according to the fifth aspect of the present invention, preferably, the lower portion of the oil storage tank functions as a catalyst sheet storage portion for accumulating the desulfurization catalyst flowing from the desulfurizer together with the liquid fuel. The flow inlet and the outlet of the liquid fuel in the oil storage tank are located above the storage portion of the catalyst sheet.

於此情形時，可將與液體燃料一起自脫硫器流出之脫硫觸媒儲存在儲油槽內，使其不流入後段之改質器內。又，由於儲油槽內之液體燃料之流入口及流出口位於觸媒片儲存部之上方，因此，藉由液體燃料之流入及流出，可抑制儲存在觸媒片儲存部之觸媒飛揚、自儲存槽流出而流入至改質器內。 In this case, the desulfurization catalyst flowing out of the desulfurizer together with the liquid fuel can be stored in the oil storage tank so that it does not flow into the reformer of the rear stage. Moreover, since the inflow port and the outflow port of the liquid fuel in the oil storage tank are located above the catalyst sheet storage portion, the inflow and outflow of the liquid fuel can suppress the flying of the catalyst stored in the catalyst sheet storage portion. The storage tank flows out and flows into the reformer.

在本發明之第5側面之燃料電池系統中，較好的是包括：油盤，其配置在儲油槽之下方；溢流管，其一方開口配置於儲油槽內，另一方開口配置在儲油槽外並且朝向下方且朝向油盤配置；以及洩漏感測器，其配置在油盤內。 In the fuel cell system according to the fifth aspect of the present invention, it is preferable that the fuel cell system includes: an oil pan disposed below the oil storage tank; and an overflow pipe having one opening disposed in the oil reservoir and the other opening being disposed in the oil reservoir Outside and facing downwards and towards the oil pan configuration; and a leakage sensor disposed within the oil pan.

於此情形時，即使因某種原因而使液體燃料充滿於儲油槽內，液體燃料亦會流過溢流管而流向油盤。並且，可利用配置在油盤內之洩漏感測器檢測出液體燃料流入至油盤內。 In this case, even if the liquid fuel is filled in the oil reservoir for some reason, the liquid fuel flows through the overflow pipe and flows to the oil pan. Moreover, the leakage sensor disposed in the oil pan can be used to detect the inflow of liquid fuel into the oil pan.

在本發明之第5側面之燃料電池系統中，較好的是包括：燃燒器，其對改質器進行加熱；以及氣體排出管線，其將自排放孔流出之流出氣體作為該燃燒器之燃燒用燃料。 In the fuel cell system of the fifth aspect of the present invention, preferably, the burner includes: a burner that heats the reformer; and a gas discharge line that uses the outflow gas flowing out from the discharge hole as the combustion of the burner Use fuel.

於此情形時，可防止自排放孔流出之流出氣體流至燃料電池系統之周圍。又，使用流出氣體作為燃燒器之燃料，因此可有助於節能。 In this case, the outflow gas flowing out of the discharge hole can be prevented from flowing to the periphery of the fuel cell system. Further, the effluent gas is used as the fuel of the burner, and thus it contributes to energy saving.

根據本發明之第5側面之燃料電池系統，即使在高壓下進行脫硫之情形時，亦可提高脫硫器之後段之設備之耐久性，從而可實現低成本並且防止性能降低。 According to the fuel cell system of the fifth aspect of the present invention, even when desulfurization is performed under high pressure, the durability of the apparatus in the subsequent stage of the desulfurizer can be improved, thereby achieving low cost and preventing performance degradation.

(本發明之第6側面) (Sixth aspect of the invention)

在燃料電池系統中，將液體燃料等作為原燃料，在改質器中對該液體燃料等進行改質而製造包含氫之改質氣體，並使該改質氣體及包含氧之氣體反應而進行發電。 In a fuel cell system, a liquid fuel or the like is used as a raw fuel, and the liquid fuel or the like is modified in a reformer to produce a reformed gas containing hydrogen, and the modified gas and the gas containing oxygen are reacted. Power generation.

然而，在使用煤油等包含硫成分之燃料作為液體燃料之情形時，改質觸媒由於與存在於液體燃料中之之硫成分接觸，因此改質觸媒會發生硫中毒，從而產生壽命縮短等性能之劣化。因此，為防止改質觸媒之劣化，燃料電池系統一般具有自液體燃料中除去硫成分之脫硫器(例如，參照日本專利特開2004-213941號公報)。 However, when a fuel containing a sulfur component such as kerosene is used as the liquid fuel, the modified catalyst is in contact with the sulfur component present in the liquid fuel, so sulfur poisoning occurs in the modified catalyst, resulting in shortened life, etc. Deterioration in performance. Therefore, in order to prevent deterioration of the reforming catalyst, the fuel cell system generally has a desulfurizer that removes a sulfur component from the liquid fuel (for example, refer to Japanese Laid-Open Patent Publication No. 2004-213941).

然而，為體現脫硫觸媒之性能，較好的是使脫硫器內之溫度為高溫(例如，200℃左右)。再者，在如此般使脫硫器內達到高溫時，會產生氣體(沼氣及氫氣等)，因此所供給之液體燃料(煤油)之流量容易降低，或液體燃料(煤油)會氣化而發生結碳(coking)(在脫硫觸媒之表面析出碳)，從而導致脫硫觸媒之耐久性容易降低，因此為抑制該等情形，較好的是脫硫器內之壓力為高壓(例如，0.5MPa左右)。 However, in order to exhibit the performance of the desulfurization catalyst, it is preferred to set the temperature in the desulfurizer to a high temperature (for example, about 200 ° C). Further, when the high temperature in the desulfurizer is reached in this way, gas (biogas, hydrogen, etc.) is generated, so that the flow rate of the supplied liquid fuel (kerosene) is liable to lower, or the liquid fuel (kerosene) is vaporized. Coking (precipitating carbon on the surface of the desulfurization catalyst) causes the durability of the desulfurization catalyst to be easily lowered. Therefore, in order to suppress such a situation, it is preferred that the pressure in the desulfurizer is high (for example, , about 0.5MPa).

然而，使脫硫器內處於高溫高壓之情形時，液體燃料之流量變大。因此，在需以極低流量(例如，1kW之燃料電池系統時為10g/min以下)輸送液體燃料之小型燃料電池系統中，存在如何將液體燃料之流量控制為較低之問題。此時，亦可考慮利用低流量泵，但低流量泵價格非常高，並未現實之選。 However, when the inside of the desulfurizer is at a high temperature and a high pressure, the flow rate of the liquid fuel becomes large. Therefore, in a small fuel cell system that needs to deliver liquid fuel at a very low flow rate (for example, 10 g/min or less in a 1 kW fuel cell system), there is a problem of how to control the flow rate of the liquid fuel to be low. At this point, it is also possible to consider the use of low-flow pumps, but the low-flow pumps are very expensive and are not realistic.

因此，本發明之第6側面目的在於提供一種可簡單且以低成本實現以低流量輸送液體燃料之燃料電池系統及改質系統。 Accordingly, a sixth aspect of the present invention is to provide a fuel cell system and a reforming system that can realize liquid fuel transportation at a low flow rate simply and at low cost.

本發明之第6側面之燃料電池系統之特徵在於包括：泵，其送出液體燃料；脫硫器，其配置在泵之下游側，用於自液體燃料中除去硫成分；毛細管，其配置在脫硫器之下游側，供藉由脫硫器除去了硫成分之液體燃料通過；改質器，其配置在毛細管之下游側，使用藉由脫硫器除去了硫成分之液體燃料生成含有氫之改質氣體；以及燃料電池堆疊，其使用藉由改質器生成之改質氣體進行發電。 A fuel cell system according to a sixth aspect of the present invention, comprising: a pump that delivers a liquid fuel; a desulfurizer disposed on a downstream side of the pump for removing sulfur components from the liquid fuel; and a capillary tube configured to be off On the downstream side of the sulfurizer, the liquid fuel through which the sulfur component is removed by the desulfurizer passes; the reformer is disposed on the downstream side of the capillary, and the liquid fuel containing the sulfur component removed by the desulfurizer generates hydrogen-containing a reformed gas; and a fuel cell stack that uses the reformed gas generated by the reformer to generate electricity.

在本發明之第6側面之燃料電池系統中，在脫硫器之下游側配置毛細管。因此，藉由適當選擇毛細管之內徑及長度，不使用高價之泵，便可使脫硫器內之壓力及液體燃料之流量達到期望之大小。其結果，可簡單且以低成本實現以低流量輸送液體燃料。 In the fuel cell system according to the sixth aspect of the present invention, the capillary is disposed on the downstream side of the desulfurizer. Therefore, by appropriately selecting the inner diameter and length of the capillary, the pressure in the desulfurizer and the flow rate of the liquid fuel can be made to a desired size without using a high-priced pump. As a result, the liquid fuel can be delivered at a low flow rate simply and at low cost.

然而，以可考慮利用節流孔、針型閥等來替代毛細管。然而，延長節流孔部分之流路存在極限，因此為減小自脫硫器被排出之高壓之液體燃料之流量，必需使節流孔部分之直徑極小。此處，在脫硫器中係利用脫硫觸媒進行液體燃料之脫硫，但有時脫硫觸媒會包含於藉由脫硫器除去了硫成分之液體燃料中。因此，在利用節流孔、針型閥等之情形時，有時自脫硫器流出之脫硫觸媒會堵塞節流孔部分之流路。 However, it is conceivable to use an orifice, a needle valve or the like instead of a capillary. However, there is a limit to extending the flow path of the orifice portion, and therefore, in order to reduce the flow rate of the high-pressure liquid fuel discharged from the desulfurizer, it is necessary to make the diameter of the orifice portion extremely small. Here, in the desulfurizer, the desulfurization catalyst is used for desulfurization of the liquid fuel, but sometimes the desulfurization catalyst is contained in the liquid fuel from which the sulfur component is removed by the desulfurizer. Therefore, in the case of using an orifice, a needle valve, or the like, the desulfurization catalyst that flows out from the desulfurizer sometimes blocks the flow path of the orifice portion.

然而，在本發明之第6側面之燃料電池系統中，如上所述般使用毛細管，因此根據毛細管之長度，可在一定程度上增大毛細管之內徑。因此，極難發生由脫硫觸媒引起之堵塞。 However, in the fuel cell system of the sixth aspect of the invention, since the capillary is used as described above, the inner diameter of the capillary can be increased to some extent depending on the length of the capillary. Therefore, it is extremely difficult to cause clogging caused by the desulfurization catalyst.

較好的是泵為恆壓泵。如此，容易管理脫硫器內之壓力。 Preferably, the pump is a constant pressure pump. In this way, it is easy to manage the pressure in the desulfurizer.

較好的是，毛細管之內徑係0.1mm~0.7mm。當毛細管之內徑未達0.1mm時，存在容易發生由脫硫觸媒堵塞毛細管之傾向。當毛細管之內徑超過0.7mm時，為一面將脫硫器內維持為高壓一面以低流量輸送液體燃料，所需之毛細管之全長變長，存在難以小型化之傾向。 Preferably, the inner diameter of the capillary is from 0.1 mm to 0.7 mm. When the inner diameter of the capillary is less than 0.1 mm, there is a tendency that the capillary is easily blocked by the desulfurization catalyst. When the inner diameter of the capillary exceeds 0.7 mm, the liquid fuel is supplied at a low flow rate while maintaining the high pressure inside the desulfurizer, and the total length of the capillary required is long, which tends to be difficult to miniaturize.

較好的是，毛細管係捲繞成螺旋狀。如此，即使於毛細管之全長變長之情形時，體積亦不易變大。 Preferably, the capillary system is wound into a spiral shape. Thus, even when the total length of the capillary is long, the volume is not easily increased.

另一方面，本發明之第6側面之改質系統之特徵在於包括：泵，其送出液體燃料；脫硫器，其配置在泵之下游側，用於自液體燃料中除去硫成分；毛細管，其配置在脫硫器之下游側，供藉由脫硫器除去了硫成分之液體燃料通過；改質器，其配置在毛細管之下游側，使用藉由脫硫器除去了硫成分之液體燃料生成含有氫之改質氣體。 In another aspect, the upgrading system of the sixth aspect of the present invention is characterized by comprising: a pump for sending liquid fuel; and a desulfurizer disposed on a downstream side of the pump for removing sulfur components from the liquid fuel; It is disposed on the downstream side of the desulfurizer for the passage of the liquid fuel from which the sulfur component is removed by the desulfurizer; the reformer is disposed on the downstream side of the capillary, and uses the liquid fuel from which the sulfur component is removed by the desulfurizer A reformed gas containing hydrogen is generated.

在本發明之第6側面之改質系統中，在脫硫器之下游側配置毛細管。因此，藉由適當選擇毛細管之內徑及長度，不使用高價之泵，便可使脫硫器內之壓力及液體燃料之流量達到期望之大小。其結果，可簡便且以低成本實現以低流量輸送液體燃料。 In the reforming system of the sixth aspect of the invention, the capillary is disposed on the downstream side of the desulfurizer. Therefore, by appropriately selecting the inner diameter and length of the capillary, the pressure in the desulfurizer and the flow rate of the liquid fuel can be made to a desired size without using a high-priced pump. As a result, the liquid fuel can be delivered at a low flow rate simply and at low cost.

然而，亦可考慮利用節流孔、針型閥等來替代毛細管。然而，延長節流孔部分之流路存在極限，因此為減小自脫硫器排出之高壓之液體燃料之流量，必需使節流孔部分之直徑極小。此處，在脫硫器中係藉由脫硫觸媒進行液體燃料之脫硫，但有時脫硫觸媒會包含於利用脫硫器除去了硫成分之液體燃料中。因此，在利用節流孔、針型閥等之情形時，有時自脫硫器流出之脫硫觸媒會堵塞節流孔部分之流路。 However, it is also conceivable to use an orifice, a needle valve or the like instead of a capillary. However, there is a limit to extending the flow path of the orifice portion, so in order to reduce the flow rate of the high-pressure liquid fuel discharged from the desulfurizer, it is necessary to make the diameter of the orifice portion extremely small. Here, in the desulfurizer, the desulfurization catalyst is used for desulfurization of the liquid fuel, but sometimes the desulfurization catalyst is contained in the liquid fuel from which the sulfur component is removed by the desulfurizer. Therefore, in the case of using an orifice, a needle valve, or the like, the desulfurization catalyst that flows out from the desulfurizer sometimes blocks the flow path of the orifice portion.

然而，在本發明之第6側面之燃料電池系統中，如上所述般使用毛細管，因此根據毛細管之長度，可在一定程度上增大毛細管之內徑。因此，極難發生由脫硫觸媒引起之堵塞。 However, in the fuel cell system of the sixth aspect of the invention, since the capillary is used as described above, the inner diameter of the capillary can be increased to some extent depending on the length of the capillary. Therefore, it is extremely difficult to cause clogging caused by the desulfurization catalyst.

較好的是泵為恆壓泵。如此，容易管理脫硫器內之壓力。 Preferably, the pump is a constant pressure pump. In this way, it is easy to manage the pressure in the desulfurizer.

較好的是毛細管之內徑係0.1mm~0.7mm。當毛細管之內徑未達0.1mm時，存在容易發生由脫硫觸媒堵塞毛細管之傾向。當毛細管之內徑超過0.7mm時，為一面將脫硫器內維持為高壓一面以低流量輸送液體燃料，所需之毛細管之全長變長，存在難以小型化之傾向。 Preferably, the inner diameter of the capillary is from 0.1 mm to 0.7 mm. When the inner diameter of the capillary is less than 0.1 mm, there is a tendency that the capillary is easily blocked by the desulfurization catalyst. When the inner diameter of the capillary exceeds 0.7 mm, the liquid fuel is supplied at a low flow rate while maintaining the high pressure inside the desulfurizer, and the total length of the capillary required is long, which tends to be difficult to miniaturize.

較好的是毛細管係捲繞成螺旋狀。如此，即使於毛細管之全長變長之情形時，體積亦不易變大。 Preferably, the capillary system is wound into a spiral shape. Thus, even when the total length of the capillary is long, the volume is not easily increased.

根據本發明之第6側面，可提供一種簡便且以低成本實現以低流量輸送液體燃料之燃料電池系統及改質系統。 According to the sixth aspect of the present invention, it is possible to provide a fuel cell system and a upgrading system which realize liquid fuel transportation at a low flow rate with ease and at low cost.

1、1a‧‧‧燃料電池系統 1, 1a‧‧‧ fuel cell system

2‧‧‧改質裝置 2‧‧‧Modification device

3‧‧‧脫硫裝置 3‧‧‧Desulfurization unit

4‧‧‧燃料電池堆疊 4‧‧‧ fuel cell stacking

5‧‧‧改質器 5‧‧‧Modifier

6‧‧‧燃燒器 6‧‧‧ burner

7‧‧‧脫硫觸媒 7‧‧‧Desulfurization catalyst

7a‧‧‧脫硫器 7a‧‧‧Desulfurizer

8‧‧‧加熱器(加熱機構) 8‧‧‧heater (heating mechanism)

9‧‧‧入口閥(液體燃料導入機構) 9‧‧‧Inlet valve (liquid fuel introduction mechanism)

11‧‧‧泵(液體燃料導入機構) 11‧‧‧ pump (liquid fuel introduction mechanism)

12‧‧‧出口閥(液體燃料導出機構) 12‧‧‧Export valve (liquid fuel export mechanism)

13‧‧‧溫度計(溫度測量機構) 13‧‧‧ Thermometer (temperature measuring mechanism)

14‧‧‧壓力計(壓力測量機構) 14‧‧‧ Pressure gauge (pressure measuring mechanism)

15‧‧‧控制部(控制機構) 15‧‧‧Control Department (Control Agency)

16、23、25‧‧‧液體燃料流通管線 16, 23, 25‧‧‧ Liquid fuel distribution pipeline

17‧‧‧空氣流通管線 17‧‧‧Air circulation pipeline

18‧‧‧液體燃料排出管線 18‧‧‧Liquid fuel discharge line

19‧‧‧儲存容器 19‧‧‧ storage container

19a‧‧‧頂壁 19a‧‧‧ top wall

19b‧‧‧底壁 19b‧‧‧ bottom wall

19c‧‧‧側壁 19c‧‧‧ side wall

20‧‧‧液面計(儲存量測量機構) 20‧‧‧liquid level meter (storage measuring mechanism)

21‧‧‧毛細管 21‧‧‧ Capillary

22、24、26‧‧‧泵 22, 24, 26‧ ‧ pumps

27‧‧‧空氣流通管線 27‧‧‧Air circulation pipeline

31‧‧‧流入管 31‧‧‧Inflow pipe

31a‧‧‧流入口 31a‧‧‧Inlet

32‧‧‧排氣孔 32‧‧‧ venting holes

33‧‧‧排氣管 33‧‧‧Exhaust pipe

34‧‧‧流出管 34‧‧‧Outflow tube

34a‧‧‧流出口 34a‧‧‧Exit

35‧‧‧浮子閥 35‧‧‧ float valve

36‧‧‧浮子 36‧‧‧Float

37‧‧‧塞子 37‧‧‧ plug

38‧‧‧觸媒片 38‧‧‧catalyst tablets

39‧‧‧觸媒片儲存部 39‧‧‧Catalyst Storage Department

40‧‧‧排出管 40‧‧‧Draining tube

41、42‧‧‧電磁閥 41, 42‧‧ ‧ solenoid valve

43‧‧‧溢流管 43‧‧‧Overflow tube

43a‧‧‧一方開口 43a‧‧‧one opening

43b‧‧‧另一方開口 43b‧‧‧The other opening

44‧‧‧油盤 44‧‧‧ oil pan

45‧‧‧洩漏感測器 45‧‧‧Leak sensor

51‧‧‧低水位感測器 51‧‧‧Low water level sensor

52‧‧‧高水位感測器 52‧‧‧High water level sensor

53‧‧‧控制部 53‧‧‧Control Department

54‧‧‧開閉控制部 54‧‧‧Opening and Control Department

55‧‧‧計時器 55‧‧‧Timer

56‧‧‧計算部 56‧‧‧ Calculation Department

57‧‧‧泵控制部 57‧‧‧Pump Control Department

M‧‧‧位置 M‧‧‧ position

R‧‧‧改質系統 R‧‧‧Modification System

S‧‧‧水位 S‧‧‧ water level

S1‧‧‧低水位 S1‧‧‧low water level

S2‧‧‧高水位 S2‧‧‧ high water level

圖1係第1實施形態之燃料電池系統之一實施形態之構成圖。 Fig. 1 is a configuration diagram showing an embodiment of a fuel cell system according to a first embodiment.

圖2係圖1之燃料電池系統所具有之脫硫裝置之構成圖。 Fig. 2 is a view showing the configuration of a desulfurization apparatus included in the fuel cell system of Fig. 1.

圖3係表示圖2之脫硫裝置之脫硫器內之液體燃料之溫度及壓力之間之關係之圖表。 Figure 3 is a graph showing the relationship between the temperature and pressure of the liquid fuel in the desulfurizer of the desulfurization apparatus of Figure 2.

圖4係表示圖2之脫硫裝置之啟動動作之流程圖。 Fig. 4 is a flow chart showing the starting operation of the desulfurization apparatus of Fig. 2.

圖5係第2實施形態之燃料電池系統之實施形態之構成圖。 Fig. 5 is a configuration diagram of an embodiment of a fuel cell system according to a second embodiment.

圖6係圖5之燃料電池系統所具有之脫硫裝置之構成圖。 Fig. 6 is a view showing the configuration of a desulfurization apparatus included in the fuel cell system of Fig. 5.

圖7係表示圖6之脫硫裝置之運轉狀態及設定溫度之間之關係之一例之圖。 Fig. 7 is a view showing an example of the relationship between the operating state and the set temperature of the desulfurization apparatus of Fig. 6.

圖8係表示圖6之脫硫裝置之動作之流程圖。 Fig. 8 is a flow chart showing the operation of the desulfurization apparatus of Fig. 6.

圖9係第3實施形態之燃料電池系統之一實施形態之構成圖。 Fig. 9 is a configuration diagram showing an embodiment of a fuel cell system according to a third embodiment.

圖10係圖9之燃料電池系統所具有之脫硫裝置之構成圖。 Fig. 10 is a view showing the configuration of a desulfurization apparatus included in the fuel cell system of Fig. 9.

圖11係表示圖10之脫硫裝置之運轉停止時之溫度及壓力之間之關係之表。 Fig. 11 is a table showing the relationship between the temperature and the pressure at the time of stopping the operation of the desulfurization apparatus of Fig. 10.

圖12係表示圖10之脫硫裝置之停止動作之流程圖。 Fig. 12 is a flow chart showing the stop operation of the desulfurization apparatus of Fig. 10.

圖13係第4實施形態之燃料電池系統之一實施形態之構成圖。 Fig. 13 is a configuration diagram showing an embodiment of a fuel cell system according to a fourth embodiment.

圖14係表示圖13之燃料電池系統之浮動開關、電磁閥及脫硫器之 壓力之關係之圖表。 Figure 14 is a diagram showing the floating switch, solenoid valve and desulfurizer of the fuel cell system of Figure 13; A chart of the relationship between stress.

圖15係概略表示第5實施形態之燃料電池系統之圖。 Fig. 15 is a view schematically showing a fuel cell system of a fifth embodiment;

圖16係表示第5實施形態之燃料電池系統所具有之儲油槽之圖。 Fig. 16 is a view showing an oil reservoir of a fuel cell system according to a fifth embodiment.

圖17係表示第5實施形態之燃料電池系統所具有之儲油槽之圖。 Fig. 17 is a view showing an oil reservoir of a fuel cell system according to a fifth embodiment.

圖18係概略表示第5實施形態之燃料電池系統之變形例之圖。 Fig. 18 is a view schematically showing a modification of the fuel cell system of the fifth embodiment.

圖19係表示第5實施形態之燃料電池系統所具有之儲油槽之變形例之圖。 Fig. 19 is a view showing a modification of the oil reservoir provided in the fuel cell system of the fifth embodiment.

圖20係表示在圖19所示之變形例中，第5實施形態之燃料電池系統所具有之控制部之圖。 Fig. 20 is a view showing a control unit included in the fuel cell system of the fifth embodiment in the modification shown in Fig. 19;

圖21係表示第5實施形態之燃料電池系統所具有之儲油槽之變形例之圖。 Fig. 21 is a view showing a modification of the oil reservoir of the fuel cell system of the fifth embodiment.

圖22係概略表示第6實施形態之燃料電池系統之圖。 Fig. 22 is a view schematically showing a fuel cell system of a sixth embodiment;

圖23係概略表示第6實施形態之燃料電池系統之另一例之圖。 Fig. 23 is a view schematically showing another example of the fuel cell system of the sixth embodiment.

(第1實施形態) (First embodiment)

以下參照圖1~圖4對第1實施形態之燃料電池系統1進行詳細說明。 Hereinafter, the fuel cell system 1 of the first embodiment will be described in detail with reference to Figs. 1 to 4 .

圖1係第1實施形態之燃料電池系統之一實施形態之構成圖。如圖1所示，燃料電池系統1包括：生成含有氫之改質氣體之改質裝置2；自供給至改質裝置2中之液體燃料中除去硫成分之脫硫裝置3；以及使用由改質裝置2生成之改質氣體進行發電之燃料電池堆疊4。燃料電池系統1例如係用作家庭用電力供給源者，自可容易獲得且可獨立儲存之觀點考慮，使用煤油作為液體燃料。 Fig. 1 is a configuration diagram showing an embodiment of a fuel cell system according to a first embodiment. As shown in FIG. 1, the fuel cell system 1 includes: a reforming device 2 for generating a reformed gas containing hydrogen; and a desulfurizing device 3 for removing a sulfur component from a liquid fuel supplied to the reforming device 2; The reformed gas generated by the mass device 2 is used to generate a fuel cell stack 4 for power generation. The fuel cell system 1 is used, for example, as a household power source, and uses kerosene as a liquid fuel from the viewpoint of being easily available and independently storageable.

改質裝置2包括：對液體燃料進行水蒸氣改質而生成改質氣體之改質器5；以及對收容在改質器5內之改質觸媒進行加熱之燃燒器6。燃燒器6藉由加熱用於促進水蒸氣改質反應之改質觸媒，將使觸媒反 應有效地發揮所需之熱供給於改質觸媒。在改質器5中，自脫硫裝置3導入之液體燃料氣化而成為原料氣體，利用改質觸媒促進原料氣體及水蒸氣(水)之間之水蒸氣改質反應，生成富氫(hydrogen rich)之改質氣體。 The reforming device 2 includes a reformer 5 that reforms a liquid fuel by steam reforming to generate a reformed gas, and a burner 6 that heats the reforming catalyst contained in the reformer 5. The burner 6 will reverse the catalyst by heating the modified catalyst for promoting the steam reforming reaction. The required heat should be effectively supplied to the modified catalyst. In the reformer 5, the liquid fuel introduced from the desulfurization device 3 is vaporized to become a raw material gas, and the reforming catalyst is used to promote the steam reforming reaction between the raw material gas and the water vapor (water) to generate hydrogen-rich gas ( Hydrogen rich) modified gas.

燃料電池堆疊4係多個電池單元堆積而構成之固體高分子型燃料電池堆疊，使用在改質裝置2中獲得之改質氣體進行發電。各電池單元具有陽極、陰極及配置在陽極與陰極之間之作為電解質之高分子離子交換膜。在各電池單元中，改質氣體被導入至陽極並且空氣被導入至陰極，藉此進行電化學發電反應。 The fuel cell stack 4 is a solid polymer fuel cell stack in which a plurality of battery cells are stacked, and the reformed gas obtained in the reforming device 2 is used for power generation. Each of the battery cells has an anode, a cathode, and a polymer ion exchange membrane as an electrolyte disposed between the anode and the cathode. In each of the battery cells, the reformed gas is introduced to the anode and the air is introduced to the cathode, thereby performing an electrochemical power generation reaction.

圖2係圖1之燃料電池系統所具有之脫硫裝置之構成圖。如圖2所示，脫硫裝置3具有收容脫硫觸媒7a之脫硫器7，該脫硫觸媒7a用於自供給至改質器5中之液體燃料中除去硫成分。脫硫觸媒7a由加熱器(加熱機構)8加熱至特定溫度。在脫硫器7之上游側設有調節向脫硫器7內導入液體燃料之導入量之入口閥(液體燃料導入機構)9。並且，在入口閥9之上游側設有將液體燃料加壓輸送至脫硫器7內之泵(液體燃料導入機構)11。另一方面，在脫硫器7之下游側設有調節來自脫硫器7內之液體燃料之導出量之出口閥(液體燃料導出機構)12。 Fig. 2 is a view showing the configuration of a desulfurization apparatus included in the fuel cell system of Fig. 1. As shown in Fig. 2, the desulfurization apparatus 3 has a desulfurizer 7 for containing a desulfurization catalyst 7a for removing sulfur components from the liquid fuel supplied to the reformer 5. The desulfurization catalyst 7a is heated by a heater (heating mechanism) 8 to a specific temperature. An inlet valve (liquid fuel introduction means) 9 for adjusting the introduction amount of the liquid fuel into the desulfurizer 7 is provided on the upstream side of the desulfurizer 7. Further, a pump (liquid fuel introduction mechanism) 11 that pressurizes the liquid fuel into the desulfurizer 7 is provided on the upstream side of the inlet valve 9. On the other hand, an outlet valve (liquid fuel discharge mechanism) 12 for regulating the amount of liquid fuel from the desulfurizer 7 is provided on the downstream side of the desulfurizer 7.

又，在脫硫器7上設有測量脫硫器7內之液體燃料之溫度之溫度計(溫度測量機構)13。並且，在脫硫器7及入口閥9之間還設有測量脫硫器7內之液體燃料之壓力之壓力計(壓力測量機構)14。控制部(控制機構)15根據由溫度計13測量之溫度及由壓力計14測量之壓力，對加熱器8、入口閥9、泵11及出口閥12進行控制。 Further, a thermometer (temperature measuring means) 13 for measuring the temperature of the liquid fuel in the desulfurizer 7 is provided in the desulfurizer 7. Further, a pressure gauge (pressure measuring means) 14 for measuring the pressure of the liquid fuel in the desulfurizer 7 is provided between the desulfurizer 7 and the inlet valve 9. The control unit (control means) 15 controls the heater 8, the inlet valve 9, the pump 11, and the outlet valve 12 based on the temperature measured by the thermometer 13 and the pressure measured by the pressure gauge 14.

如圖1所示，脫硫裝置3與供硫成分被除去之液體燃料流通之液體燃料流通管線16之一端相連接，液體燃料流通管線16之另一端與配置在脫硫裝置3上方之儲存容器19之側壁相連接。儲存容器19之底壁與液體燃料流通管線23、液體燃料流通管線25相連接，在該液體燃料流 通管線23上設有用於將儲存在儲存容器19內之下方之液體燃料導入至改質器5中之泵22，在該液體燃料流通管線25上設有用於將該液體燃料導入至燃燒器6中之泵24。再者，燃燒器6與設有用於將空氣導入燃燒器6中之泵26之空氣流通管線27相連接。如此，藉由將液體燃料暫時儲存在儲存容器19中，可使泵22對改質器5之液體燃料之供給及泵24對燃燒器6之液體燃料之供給穩定化。 As shown in Fig. 1, the desulfurization device 3 is connected to one end of a liquid fuel circulation line 16 through which a liquid fuel from which a sulfur component is removed, and the other end of the liquid fuel circulation line 16 and a storage container disposed above the desulfurization device 3. The side walls of 19 are connected. The bottom wall of the storage container 19 is connected to the liquid fuel circulation line 23 and the liquid fuel circulation line 25, in which the liquid fuel flow The through line 23 is provided with a pump 22 for introducing the liquid fuel stored below the storage container 19 into the reformer 5, and the liquid fuel circulation line 25 is provided for introducing the liquid fuel to the burner 6. In the pump 24. Further, the burner 6 is connected to an air flow line 27 provided with a pump 26 for introducing air into the burner 6. Thus, by temporarily storing the liquid fuel in the storage container 19, the supply of the liquid fuel to the reformer 5 by the pump 22 and the supply of the liquid fuel to the burner 6 by the pump 24 can be stabilized.

在如上所述般構成之燃料電池系統1中，液體燃料首先被導入至脫硫裝置3之脫硫器7中，在高溫、高壓之狀態下，藉由脫硫觸媒7a除去硫成分。自脫硫器7導出之液體燃料經由液體燃料流通管線16而儲存至儲存容器19中。被儲存至儲存容器19中之液體燃料經由液體燃料流通管線23而導入至改質器5中。此時，液體燃料經由液體燃料流通管線25而導入至燃燒器6中，並且空氣經由空氣流通管線27而導入至燃燒器6中。由此，在改質器5中，改質觸媒被進行燃燒之燃燒器6加熱，使用液體燃料而生成改質氣體。在改質器5中生成之改質氣體被導入至燃料電池堆疊4中，在燃料電池堆疊4中，使用改質氣體進行發電。 In the fuel cell system 1 configured as described above, the liquid fuel is first introduced into the desulfurizer 7 of the desulfurization apparatus 3, and the sulfur component is removed by the desulfurization catalyst 7a under high temperature and high pressure. The liquid fuel derived from the desulfurizer 7 is stored in the storage container 19 via the liquid fuel circulation line 16. The liquid fuel stored in the storage container 19 is introduced into the reformer 5 via the liquid fuel circulation line 23. At this time, the liquid fuel is introduced into the combustor 6 via the liquid fuel circulation line 25, and the air is introduced into the combustor 6 via the air flow line 27. Thereby, in the reformer 5, the reforming catalyst is heated by the burner 6 that performs combustion, and the reformed gas is generated using the liquid fuel. The reformed gas generated in the reformer 5 is introduced into the fuel cell stack 4, and in the fuel cell stack 4, the reformed gas is used for power generation.

繼而，說明脫硫裝置3之動作。圖3係表示圖2之脫硫裝置之脫硫器內之液體燃料之溫度及壓力之間之關係之圖表，圖4係表示圖2之脫硫裝置之啟動動作之流程圖。 Next, the operation of the desulfurization device 3 will be described. Fig. 3 is a graph showing the relationship between the temperature and pressure of the liquid fuel in the desulfurizer of the desulfurization apparatus of Fig. 2, and Fig. 4 is a flow chart showing the startup operation of the desulfurization apparatus of Fig. 2.

如圖3所示，控制部15將脫硫器7內之液體燃料之各溫度時之、脫硫器7內之液體燃料之壓力之目標值存儲作為資料表。該壓力之目標值係設定為各溫度時之液體燃料之飽和蒸氣壓以上且為脫硫器7之耐壓以下。亦即，根據脫硫器7內之液體燃料之溫度，只要將脫硫器7內之液體燃料之壓力維持為目標值，便可防止液體燃料之氣化。 As shown in FIG. 3, the control unit 15 stores the target value of the pressure of the liquid fuel in the desulfurizer 7 at each temperature of the liquid fuel in the desulfurizer 7 as a data table. The target value of the pressure is set to be equal to or higher than the saturated vapor pressure of the liquid fuel at each temperature and equal to or less than the withstand voltage of the desulfurizer 7. That is, according to the temperature of the liquid fuel in the desulfurizer 7, as long as the pressure of the liquid fuel in the desulfurizer 7 is maintained at a target value, vaporization of the liquid fuel can be prevented.

如圖4所示，脫硫裝置3之啟動動作開始時，控制部15對由溫度計13測量之溫度、即脫硫器7內之液體燃料之溫度是否比A高進行判斷 (步驟S11)。於其結果為脫硫器7內之液體燃料之溫度比A低之情形時，為加熱脫硫器7內之脫硫觸媒7a，控制部15使加熱器8動作(步驟S12)，返回至步驟S11之判斷處理。 As shown in FIG. 4, when the start-up operation of the desulfurization device 3 is started, the control unit 15 determines whether the temperature measured by the thermometer 13, that is, the temperature of the liquid fuel in the desulfurizer 7, is higher than A. (Step S11). When the temperature of the liquid fuel in the desulfurizer 7 is lower than A as a result, the desulfurization catalyst 7a in the desulfurizer 7 is heated, and the control unit 15 operates the heater 8 (step S12), and returns to The judgment processing of step S11.

於步驟S11之判斷處理之結果為脫硫器7內之液體燃料之溫度比A高之情形時，控制部15對由壓力計14測量之壓力、即脫硫器7內之液體燃料之壓力是否比X高進行判斷(步驟S13)。於其結果為脫硫器7內之液體燃料之壓力比X低之情形時，為將液體燃料導入至脫硫器7內，控制部15使泵11動作並且開啟入口閥9(步驟S14)，進而使加熱器8停止(步驟S15)，返回至步驟S13之判斷處理。 When the result of the determination processing in step S11 is that the temperature of the liquid fuel in the desulfurizer 7 is higher than A, the pressure measured by the pressure gauge 14 by the control unit 15 or the pressure of the liquid fuel in the desulfurizer 7 is The judgment is made higher than X (step S13). When the pressure of the liquid fuel in the desulfurizer 7 is lower than X, the control unit 15 operates the pump 11 and opens the inlet valve 9 (step S14), in order to introduce the liquid fuel into the desulfurizer 7. Further, the heater 8 is stopped (step S15), and the process returns to the determination process of step S13.

於步驟S13之判斷處理結果為脫硫器7內之液體燃料之壓力比X高之情形時，控制部15使泵11停止並且關閉入口閥9(步驟S16)。然後，控制部15對由溫度計13測量之溫度、即脫硫器7內之液體燃料之溫度是否比B(>A)高進行判斷(步驟S17)。於其結果為脫硫器7內之液體燃料之溫度比B低之情形時，為加熱脫硫器7內之脫硫觸媒7a，控制部15使加熱器8動作(步驟S18)，返回至步驟S17之判斷處理。 When the result of the determination in step S13 is that the pressure of the liquid fuel in the desulfurizer 7 is higher than X, the control unit 15 stops the pump 11 and closes the inlet valve 9 (step S16). Then, the control unit 15 determines whether or not the temperature measured by the thermometer 13, that is, the temperature of the liquid fuel in the desulfurizer 7, is higher than B (>A) (step S17). When the temperature of the liquid fuel in the desulfurizer 7 is lower than B as a result, the desulfurization catalyst 7a in the desulfurizer 7 is heated, and the control unit 15 operates the heater 8 (step S18), and returns to The judgment processing of step S17.

於步驟S17之判斷處理結果為脫硫器7內之液體燃料之溫度比B高之情形時，控制部15對由壓力計14測量之壓力、即脫硫器7內之液體燃料之壓力是否比Y(>X)高進行判斷(步驟S19)。於其結果為脫硫器7內之液體燃料壓力比Y低之情形時，為將液體燃料導入至脫硫器7內，控制部15使泵11動作並且開啟入口閥9(步驟S20)，進而使加熱器8停止(步驟S21)，返回至步驟S19之判斷處理。 When the result of the determination in step S17 is that the temperature of the liquid fuel in the desulfurizer 7 is higher than B, the control unit 15 compares the pressure measured by the pressure gauge 14, that is, the pressure of the liquid fuel in the desulfurizer 7 Y (>X) is judged high (step S19). When the liquid fuel pressure in the desulfurizer 7 is lower than Y, the control unit 15 operates the pump 11 and opens the inlet valve 9 (step S20), in order to introduce the liquid fuel into the desulfurizer 7. The heater 8 is stopped (step S21), and the process returns to the determination process of step S19.

於步驟S19之判斷處理結果為脫硫器7內之液體燃料之壓力比Y高之情形時，控制部15使泵11停止並且關閉入口閥9(步驟S22)。然後，控制部15對由溫度計13測量之溫度、即脫硫器7內之液體燃料之溫度是否比C(>B)高進行判斷(步驟S23)。於其結果為脫硫器7內之液體燃料之溫度比C低之情形時，為加熱脫硫器7內之脫硫觸媒7a，控制部15 使加熱器8動作(步驟S24)，返回至步驟S23之判斷處理。 When the result of the determination in step S19 is that the pressure of the liquid fuel in the desulfurizer 7 is higher than Y, the control unit 15 stops the pump 11 and closes the inlet valve 9 (step S22). Then, the control unit 15 determines whether or not the temperature measured by the thermometer 13, that is, the temperature of the liquid fuel in the desulfurizer 7, is higher than C (> B) (step S23). When the temperature of the liquid fuel in the desulfurizer 7 is lower than C, the desulfurization catalyst 7a in the desulfurizer 7 is heated, and the control unit 15 The heater 8 is operated (step S24), and the process returns to the determination process of step S23.

於步驟S23之判斷處理結果為脫硫器7內之液體燃料之溫度比C高之情形時，控制部15對由壓力計14測量之壓力、即脫硫器7內之液體燃料壓力是否比Z(>Y)高進行判斷(步驟S25)。於其結果為脫硫器7內之液體燃料之壓力比Z低之情形時，為將液體燃料導入至脫硫器7內，控制部15使泵11動作並且開啟入口閥9(步驟S26)，進而使加熱器8停止(步驟S27)，返回至步驟S25之判斷處理。 When the result of the determination in step S23 is that the temperature of the liquid fuel in the desulfurizer 7 is higher than C, the control unit 15 determines whether the pressure measured by the pressure gauge 14, that is, the liquid fuel pressure in the desulfurizer 7, is greater than Z. (>Y) High judgment (step S25). When the pressure of the liquid fuel in the desulfurizer 7 is lower than Z, the control unit 15 operates the pump 11 and opens the inlet valve 9 (step S26), in order to introduce the liquid fuel into the desulfurizer 7. Further, the heater 8 is stopped (step S27), and the process returns to the determination process of step S25.

於步驟S25之判斷處理結果為脫硫器7內之液體燃料之壓力比Z高之情形時，控制部15使泵11停止並且關閉入口閥9(步驟S28)。然後，控制部15對由溫度計13測量之溫度、即脫硫器7內之液體燃料之溫度是否比D(>C)高進行判斷(步驟S29)。於其結果為脫硫器7內之液體燃料之溫度比D低之情形時，為加熱脫硫器7內之脫硫觸媒7a，控制部15使加熱器8動作(步驟S30)，返回至步驟S29之判斷處理。 When the result of the determination in step S25 is that the pressure of the liquid fuel in the desulfurizer 7 is higher than Z, the control unit 15 stops the pump 11 and closes the inlet valve 9 (step S28). Then, the control unit 15 determines whether or not the temperature measured by the thermometer 13, that is, the temperature of the liquid fuel in the desulfurizer 7, is higher than D (>C) (step S29). When the temperature of the liquid fuel in the desulfurizer 7 is lower than D, the heating unit 8a in the desulfurizer 7 is heated, and the control unit 15 operates the heater 8 (step S30), and returns to The judgment processing of step S29.

於步驟S29之判斷處理結果為脫硫器7內之液體燃料之溫度比D高之情形時，在該溫度下進行脫硫，為將硫成分被除去之液體燃料供給至改質裝置2中，使泵11動作並開啟入口閥9及出口閥12，脫硫裝置3之啟動動作結束。 When the result of the determination in step S29 is that the temperature of the liquid fuel in the desulfurizer 7 is higher than D, the desulfurization is performed at the temperature, and the liquid fuel from which the sulfur component is removed is supplied to the reforming device 2, When the pump 11 is operated and the inlet valve 9 and the outlet valve 12 are opened, the start-up operation of the desulfurization device 3 is completed.

如上所說明般，在燃料電池系統1之脫硫裝置3中，控制部15對加熱器8、入口閥9、泵11及出口閥12進行控制，使得由溫度計13測量之溫度、即脫硫器7內之液體燃料之溫度達到特定溫度，由壓力計14測量之壓力、即脫硫器7內之液體燃料之壓力達到特定溫度下之液體燃料之飽和蒸氣壓以上且為脫硫器之耐壓以下之特定壓力(即目標值)。其不僅在脫硫裝置3之啟動動作時，在脫硫裝置3之穩定動作時及停止動作時亦同樣。因此，即使使脫硫器7內之液體燃料之溫度上升，亦可防止液體燃料氣化，其結果，可實現高效率之脫硫及抑制脫硫觸媒7a之劣化。 As described above, in the desulfurization device 3 of the fuel cell system 1, the control unit 15 controls the heater 8, the inlet valve 9, the pump 11, and the outlet valve 12 so that the temperature measured by the thermometer 13, that is, the desulfurizer The temperature of the liquid fuel in 7 reaches a specific temperature, and the pressure measured by the pressure gauge 14, that is, the pressure of the liquid fuel in the desulfurizer 7 reaches the saturated vapor pressure of the liquid fuel at a specific temperature and is the pressure resistance of the desulfurizer. The specific pressure below (ie the target value). This is the same not only when the desulfurization device 3 is activated, but also during the steady operation of the desulfurization device 3 and when the operation is stopped. Therefore, even if the temperature of the liquid fuel in the desulfurizer 7 is increased, the liquid fuel can be prevented from being vaporized, and as a result, high-efficiency desulfurization and deterioration of the desulfurization catalyst 7a can be achieved.

又，在使由壓力計14測量之壓力上升之情形時，控制部15使泵11動作並開啟入口閥9而使液體燃料之導入量增加，並且關閉出口閥12而使液體燃料之導出量減少。另一方面，在使由壓力計14測量之壓力降低之情形時，控制部15使泵11停止並關閉入口閥9而使液體燃料之導入量減少，並且開啟出口閥12使液體燃料之導出量增加。藉此，可迅速且確實地使由壓力計14測量之壓力、即脫硫器7內之液體燃料之壓力上升或降低。又，所謂「關閉入口閥9(或出口閥12)」不僅係指完全關閉而流量為0之情形，亦包括未完全關閉而流量減少之情形。 Further, when the pressure measured by the pressure gauge 14 is raised, the control unit 15 operates the pump 11 and opens the inlet valve 9 to increase the introduction amount of the liquid fuel, and closes the outlet valve 12 to reduce the amount of liquid fuel to be discharged. . On the other hand, when the pressure measured by the pressure gauge 14 is lowered, the control portion 15 stops the pump 11 and closes the inlet valve 9 to reduce the introduction amount of the liquid fuel, and opens the outlet valve 12 to cause the liquid fuel to be discharged. increase. Thereby, the pressure measured by the pressure gauge 14, that is, the pressure of the liquid fuel in the desulfurizer 7 can be quickly and surely increased or decreased. Further, the term "closing the inlet valve 9 (or the outlet valve 12)" means not only the case where the flow rate is zero when it is completely closed, but also the case where the flow rate is not completely closed and the flow rate is reduced.

本發明之第1側面不限定於上述實施形態。 The first aspect of the present invention is not limited to the above embodiment.

例如，燃料電池堆疊4不限於固體高分子型燃料電池堆疊，亦可為固體氧化物型燃料電池堆疊等。 For example, the fuel cell stack 4 is not limited to a solid polymer fuel cell stack, and may be a solid oxide fuel cell stack or the like.

又，改質器5不限於進行水蒸氣改質之改質器，亦可為進行部分氧化改質、自身熱改質之改質器。改質器5之改質方法除根據煤油之特性而設以外，還根據汽油、石腦油、輕油、甲醇、乙醇、DME(二甲醚)、利用生物物質之生物燃料等液體燃料之特性而設。 Further, the reformer 5 is not limited to a reformer that performs steam reforming, and may be a reformer that performs partial oxidation reforming and self-heat reforming. The reforming method of the reformer 5 is based on the characteristics of kerosene, and is based on the characteristics of liquid fuels such as gasoline, naphtha, light oil, methanol, ethanol, DME (dimethyl ether), biofuels using biomass, and the like. And set.

(第2實施形態) (Second embodiment)

以下參照圖5~圖8對第2實施形態之燃料電池系統1進行詳細說明。 Hereinafter, the fuel cell system 1 of the second embodiment will be described in detail with reference to Figs. 5 to 8 .

圖5係第2實施形態之燃料電池系統1之一實施形態之構成圖。如圖5所示，燃料電池系統1包括：生成含有氫之改質氣體之改質裝置2；自供給至改質裝置2中之液體燃料中除去硫成分之脫硫裝置3；以及使用由改質裝置2生成之改質氣體進行發電之燃料電池堆疊4。燃料電池系統1例如係用作家庭用之電力供給源者，自可容易獲得且可獨立儲存之觀點考慮，使用煤油作為液體燃料。 Fig. 5 is a configuration diagram of an embodiment of a fuel cell system 1 according to a second embodiment. As shown in FIG. 5, the fuel cell system 1 includes: a reforming device 2 for generating a reformed gas containing hydrogen; and a desulfurizing device 3 for removing a sulfur component from the liquid fuel supplied to the reforming device 2; The reformed gas generated by the mass device 2 is used to generate a fuel cell stack 4 for power generation. The fuel cell system 1 is used, for example, as a power source for household use, and kerosene is used as a liquid fuel from the viewpoint of being easily available and independently storageable.

改質裝置2具有對液體燃料進行水蒸氣改質而生成改質氣體之改質器5及對收容在改質器5內之改質觸媒進行加熱之燃燒器6。燃燒器6 藉由加熱用於促進水蒸氣改質反應之改質觸媒，將使觸媒反應有效地發揮所需之熱供給於改質觸媒。在改質器5中，自脫硫裝置3導入之液體燃料氣化而成為原料氣體，利用改質觸媒促進原料氣體及水蒸氣(水)之間之水蒸氣改質反應，生成富氫之改質氣體。 The reforming device 2 includes a reformer 5 that reforms a liquid fuel by steam reforming to generate a reformed gas, and a combustor 6 that heats the reforming catalyst contained in the reformer 5. Burner 6 By heating the reforming catalyst for promoting the steam reforming reaction, the catalyst reaction is efficiently supplied to the reforming catalyst. In the reformer 5, the liquid fuel introduced from the desulfurization device 3 is vaporized to become a raw material gas, and the reforming catalyst is used to promote the steam reforming reaction between the raw material gas and the water vapor (water) to generate hydrogen-rich gas. Modified gas.

燃料電池堆疊4係多個電池單元堆積而構成之固體高分子型燃料電池堆疊，使用在改質裝置2獲得之改質氣體進行發電。各電池單元具有陽極、陰極及配置在陽極與陰極之間之作為電解質之高分子離子交換膜。在各電池單元中，改質氣體被導入至陽極並且空氣被導入至陰極，從而進行電化學之發電反應。 The fuel cell stack 4 is a solid polymer fuel cell stack in which a plurality of battery cells are stacked, and the reformed gas obtained by the reforming device 2 is used for power generation. Each of the battery cells has an anode, a cathode, and a polymer ion exchange membrane as an electrolyte disposed between the anode and the cathode. In each of the battery cells, the reformed gas is introduced to the anode and the air is introduced to the cathode to perform an electrochemical power generation reaction.

圖6係圖5之燃料電池系統所具有之脫硫裝置之構成圖。如圖6所示，脫硫裝置3具有收容脫硫觸媒7a之脫硫器7，該脫硫觸媒7a用於自供給至改質器5中之液體燃料中除去硫成分。脫硫觸媒7a由加熱器(加熱機構)8加熱至特定溫度。在脫硫器7之上游側設有調節向脫硫器7內導入液體燃料之導入量之入口閥(液體燃料導入機構)9。並且，在入口閥9之上游側設有將液體燃料加壓輸送至脫硫器7內之泵(液體燃料導入機構)11。另一方面，在脫硫器7之下游側設有調節來自脫硫器7內之液體燃料之導出量之出口閥(液體燃料導出機構)12。 Fig. 6 is a view showing the configuration of a desulfurization apparatus included in the fuel cell system of Fig. 5. As shown in Fig. 6, the desulfurization apparatus 3 has a desulfurizer 7 for containing a desulfurization catalyst 7a for removing sulfur components from the liquid fuel supplied to the reformer 5. The desulfurization catalyst 7a is heated by a heater (heating mechanism) 8 to a specific temperature. An inlet valve (liquid fuel introduction means) 9 for adjusting the introduction amount of the liquid fuel into the desulfurizer 7 is provided on the upstream side of the desulfurizer 7. Further, a pump (liquid fuel introduction mechanism) 11 that pressurizes the liquid fuel into the desulfurizer 7 is provided on the upstream side of the inlet valve 9. On the other hand, an outlet valve (liquid fuel discharge mechanism) 12 for regulating the amount of liquid fuel from the desulfurizer 7 is provided on the downstream side of the desulfurizer 7.

又，在脫硫器7上設有測量脫硫器7內之液體燃料之溫度之溫度計(溫度測量機構)13。並且，在脫硫器7及入口閥9之間設有測量脫硫器7內之液體燃料之壓力之壓力計(壓力測量機構)14。在輸出特定之信號時，控制部(控制機構)15根據該信號對加熱器8、入口閥9、泵11及出口閥12進行控制。再者，所謂特定信號係啟動信號、停止信號、暫停信號、重新開始運轉信號。 Further, a thermometer (temperature measuring means) 13 for measuring the temperature of the liquid fuel in the desulfurizer 7 is provided in the desulfurizer 7. Further, a pressure gauge (pressure measuring means) 14 for measuring the pressure of the liquid fuel in the desulfurizer 7 is provided between the desulfurizer 7 and the inlet valve 9. When a specific signal is output, the control unit (control means) 15 controls the heater 8, the inlet valve 9, the pump 11, and the outlet valve 12 based on the signal. Furthermore, the specific signal is a start signal, a stop signal, a pause signal, and a restart operation signal.

如圖5所示，脫硫裝置3與供硫成分被除去之液體燃料流通之液體燃料流通管線16之一端相連接，液體燃料流通管線16之另一端與配置在脫硫裝置3上方之儲存容器19之側壁相連接。儲存容器19中設有測 量儲存量之液面計(leveller)(儲存量測量機構)20。液面計20在儲存容器19中之儲存量達到第1儲存量時，向控制部15輸出暫停信號，在儲存容器19中之儲存量減少至比第1儲存量低位之第2儲存量時，向控制部15輸出重新開始運轉信號。 As shown in FIG. 5, the desulfurization device 3 is connected to one end of the liquid fuel circulation line 16 through which the liquid fuel from which the sulfur component is removed, and the other end of the liquid fuel circulation line 16 and the storage container disposed above the desulfurization device 3. The side walls of 19 are connected. The storage container 19 is provided with a test A leveller (storage measuring mechanism) 20 of the amount of storage. When the storage amount in the storage container 19 reaches the first storage amount, the liquid level gauge 20 outputs a pause signal to the control unit 15, and when the storage amount in the storage container 19 is reduced to the second storage amount lower than the first storage amount, The restart operation signal is output to the control unit 15.

又，儲存容器19之底壁與液體燃料流通管線23、液體燃料流通管線25相連接，該液體燃料流通管線23上設有用於將儲存在儲存容器19內下方之液體燃料導入至改質器5中之泵22，該液體燃料流通管線25上設有用於將該液體燃料導入至燃燒器6中之泵24。再者，燃燒器6與設有用於將空氣導入至燃燒器6中之泵26之空氣流通管線27相連接。如此，藉由將液體燃料暫時儲存在儲存容器19中，可使泵22對改質器5之液體燃料之供給及泵24對燃燒器6之液體燃料之供給穩定化。 Further, the bottom wall of the storage container 19 is connected to the liquid fuel circulation line 23 and the liquid fuel circulation line 25, and the liquid fuel circulation line 23 is provided with a liquid fuel for introducing the liquid fuel stored in the storage container 19 to the reformer 5 In the pump 22, the liquid fuel circulation line 25 is provided with a pump 24 for introducing the liquid fuel into the burner 6. Further, the burner 6 is connected to an air flow line 27 provided with a pump 26 for introducing air into the burner 6. Thus, by temporarily storing the liquid fuel in the storage container 19, the supply of the liquid fuel to the reformer 5 by the pump 22 and the supply of the liquid fuel to the burner 6 by the pump 24 can be stabilized.

在如上所述般構成之燃料電池系統1中，液體燃料首先被導入至脫硫裝置3之脫硫器7中，在高溫、高壓之狀態下，利用脫硫觸媒7a除去硫成分。自脫硫器7被導出之液體燃料經由液體燃料流通管線16而儲存至儲存容器19中。被儲存至儲存容器19中之液體燃料經由液體燃料流通管線23而導入至改質器5中。此時，液體燃料經由液體燃料流通管線25而導入至燃燒器6中，並且空氣經由空氣流通管線27而導入至燃燒器6中。由此，在改質器5中，改質觸媒被進行燃燒之燃燒器6加熱，使用液體燃料而生成改質氣體。在改質器5中生成之改質氣體被導入至燃料電池堆疊4中，在燃料電池堆疊4中，使用改質氣體進行發電。 In the fuel cell system 1 configured as described above, the liquid fuel is first introduced into the desulfurizer 7 of the desulfurization apparatus 3, and the sulfur component is removed by the desulfurization catalyst 7a under high temperature and high pressure. The liquid fuel derived from the desulfurizer 7 is stored in the storage container 19 via the liquid fuel circulation line 16. The liquid fuel stored in the storage container 19 is introduced into the reformer 5 via the liquid fuel circulation line 23. At this time, the liquid fuel is introduced into the combustor 6 via the liquid fuel circulation line 25, and the air is introduced into the combustor 6 via the air flow line 27. Thereby, in the reformer 5, the reforming catalyst is heated by the burner 6 that performs combustion, and the reformed gas is generated using the liquid fuel. The reformed gas generated in the reformer 5 is introduced into the fuel cell stack 4, and in the fuel cell stack 4, the reformed gas is used for power generation.

繼而，說明脫硫裝置3之動作。圖7係表示圖6之脫硫裝置之運轉狀態及設定溫度之間之關係之一例之圖，圖8係表示圖6之脫硫裝置之動作之流程圖。 Next, the operation of the desulfurization device 3 will be described. Fig. 7 is a view showing an example of the relationship between the operating state and the set temperature of the desulfurizing apparatus of Fig. 6, and Fig. 8 is a flow chart showing the operation of the desulfurizing apparatus of Fig. 6.

如圖7所示，控制部15將各運轉狀態之脫硫器7內之溫度之目標值存儲作為資料表。溫度之目標值例如在通常運轉時係190℃~210℃(可 促進脫硫觸媒7a之觸媒反應之特定脫硫溫度：溫度A)，暫停時係180℃~190℃(溫度B)。暫停時之溫度B(特定溫度)係設定為比停止時之溫度(5℃~35℃)高且比通常運轉時之溫度A低。 As shown in Fig. 7, the control unit 15 stores the target value of the temperature in the desulfurizer 7 in each operating state as a data table. The target value of the temperature is, for example, 190 ° C to 210 ° C during normal operation ( The specific desulfurization temperature for promoting the catalytic reaction of the desulfurization catalyst 7a: temperature A), and the suspension is 180 ° C to 190 ° C (temperature B). The temperature B (specific temperature) at the time of suspension is set to be higher than the temperature at the time of stop (5 ° C to 35 ° C) and lower than the temperature A during normal operation.

如圖8所示，在脫硫裝置3啟動之通常運轉時，控制部15對是否自液面計20輸入有暫停信號進行判斷(步驟S11)。於其結果為輸入有暫停信號之情形時，為停止向脫硫器7內導入液體燃料，控制部15使泵11停止並關閉入口閥9及出口閥12(步驟S12)。然後，控制部15控制加熱器8，使得脫硫器7內之液體燃料之溫度達到溫度B(步驟S13)。 As shown in FIG. 8, when the desulfurization apparatus 3 is normally operated, the control unit 15 determines whether or not a pause signal is input from the liquid level gauge 20 (step S11). When the result is that a pause signal is input, the control unit 15 stops the pump 11 and closes the inlet valve 9 and the outlet valve 12 (step S12) in order to stop the introduction of the liquid fuel into the desulfurizer 7. Then, the control unit 15 controls the heater 8 so that the temperature of the liquid fuel in the desulfurizer 7 reaches the temperature B (step S13).

步驟S13之處理後，控制部15對是否自液面計20輸入有重新開始運轉信號進行判斷(步驟S14)。於其結果為輸入有重新開始運轉信號之情形時，控制部15控制加熱器8，使得脫硫器7內之液體燃料之溫度達到溫度A(步驟S15)。然後，以溫度A進行脫硫，為將硫成分被除去之液體燃料再供給至改質裝置2中，使泵11動作並且開啟入口閥9及出口閥12(步驟S16)，返回至步驟S11之判斷處理。另一方面，在步驟S17中，於未輸入有重新開始運轉信號之情形時，反覆該處理直至輸入有重新開始運轉信號。 After the process of step S13, the control unit 15 determines whether or not the restart operation signal is input from the liquid level gauge 20 (step S14). When the result is that the restart operation signal is input, the control unit 15 controls the heater 8 so that the temperature of the liquid fuel in the desulfurizer 7 reaches the temperature A (step S15). Then, the desulfurization is performed at the temperature A, and the liquid fuel from which the sulfur component is removed is supplied to the reforming device 2, the pump 11 is operated, and the inlet valve 9 and the outlet valve 12 are opened (step S16), and the process returns to step S11. Judgment processing. On the other hand, in the case where the restart operation signal is not input in step S17, the process is repeated until the restart operation signal is input.

另一方面，於步驟S11之判斷處理結果為未輸入有暫停信號之情形時，控制部15對是否輸入有停止信號進行判斷(步驟S17)。於其結果為輸入有停止信號之情形時，控制部15使泵11停止並關閉入口閥9及出口閥12(步驟S18)，進而使加熱器8停止(步驟S19)，脫硫裝置3之運轉結束。另一方面，於未輸入有停止信號之情形時，返回至步驟S11之判斷處理。又，藉由按下用於使脫硫裝置3之動作停止之例如按鈕，而將停止信號輸入至控制部15中。 On the other hand, if the result of the determination processing in step S11 is that the pause signal is not input, the control unit 15 determines whether or not the stop signal is input (step S17). When the result is that a stop signal is input, the control unit 15 stops the pump 11 and closes the inlet valve 9 and the outlet valve 12 (step S18), and further stops the heater 8 (step S19), and the operation of the desulfurization device 3 is performed. End. On the other hand, when the stop signal is not input, the process returns to the determination process of step S11. Further, by pressing a button for stopping the operation of the desulfurizer 3, for example, a stop signal is input to the control unit 15.

如上說明般，在燃料電池系統1之脫硫裝置3中，在自液面計20輸入有暫停信號之情形時，控制部15對入口閥9、泵11及出口閥12進行控制，以停止自脫硫器7內向儲存容器19供給液體燃料。此時，控制 部15控制加熱器8，使得由溫度計13測量之溫度、即脫硫器7內之液體燃料之溫度被保持為比常溫高且比通常運轉時之溫度A低之特定溫度B(即目標值)。藉此，與使脫硫裝置3停止而使溫度降低至常溫之情形相比，加熱至通常運轉時之溫度A、即特定脫硫溫度之時間被縮短，因此可謀求縮短直至再啟動為止之時間。 As described above, in the desulfurization device 3 of the fuel cell system 1, when a pause signal is input from the liquid level gauge 20, the control unit 15 controls the inlet valve 9, the pump 11, and the outlet valve 12 to stop the self. The desulfurizer 7 supplies the liquid fuel to the storage container 19. At this point, control The portion 15 controls the heater 8 such that the temperature measured by the thermometer 13, that is, the temperature of the liquid fuel in the desulfurizer 7, is maintained at a specific temperature B (i.e., a target value) which is higher than the normal temperature and lower than the temperature A during the normal operation. . Thereby, compared with the case where the desulfurization apparatus 3 is stopped and the temperature is lowered to normal temperature, the time until the temperature A of the normal operation, that is, the specific desulfurization temperature is shortened, the time until restarting can be shortened. .

又，如圖7所示，藉由使暫停時之溫度B成為比通常運轉時之溫度A低之溫度，可謀求減少能量消耗。並且，藉由在暫停時不使溫度B降低至常溫，可防止由與通常運轉時之溫差引起之脫硫觸媒7a之劣化。 Further, as shown in FIG. 7, by setting the temperature B at the time of the pause to a temperature lower than the temperature A during the normal operation, it is possible to reduce the energy consumption. Further, by not lowering the temperature B to the normal temperature at the time of suspension, deterioration of the desulfurization catalyst 7a caused by the temperature difference from the normal operation can be prevented.

又，具有暫時儲存液體燃料之儲存容器19，於儲存容器19之儲存量達到第1儲存量之情形時，液面計20向控制部15輸出暫停信號。另一方面，於儲存容器19之儲存量減少為比第1儲存量低位之第2儲存量之情形時，液面計20向控制部15輸出重新開始運轉信號。藉此，可防止例如儲存量超量導致之儲存容器19之破損等。又，在減少至比第1儲存量低位之第2儲存量之情形時，輸出重新開始運轉信號，脫硫裝置3之動作重新開始，因此可謀求作業之效率化。 Further, the storage container 19 for temporarily storing the liquid fuel outputs a pause signal to the control unit 15 when the storage amount of the storage container 19 reaches the first storage amount. On the other hand, when the storage amount of the storage container 19 is reduced to the second storage amount lower than the first storage amount, the liquid level meter 20 outputs a restart operation signal to the control unit 15. Thereby, it is possible to prevent breakage of the storage container 19 caused by, for example, an excessive amount of storage. Further, when the second storage amount lower than the first storage amount is reduced, the restart operation signal is output, and the operation of the desulfurization device 3 is restarted, so that the work efficiency can be improved.

本發明之第2側面不限於上述實施形態。 The second aspect of the present invention is not limited to the above embodiment.

例如，在輸入有暫停信號之情形時，亦可不關閉入口閥9及出口閥12這兩者，而僅關閉入口閥9。 For example, when the pause signal is input, both the inlet valve 9 and the outlet valve 12 may not be closed, and only the inlet valve 9 may be closed.

又，暫停信號及重新開始運轉信號亦可不自液面計20輸入，而例如藉由押下按鈕來輸入。 Further, the pause signal and the restart operation signal may not be input from the liquid level gauge 20, but may be input, for example, by pressing a button.

又，燃料電池堆疊4不限於固體高分子型燃料電池堆疊，亦可為固體氧化物型燃料電池堆疊等。 Further, the fuel cell stack 4 is not limited to a solid polymer fuel cell stack, and may be a solid oxide fuel cell stack or the like.

又，改質器5不限於進行水蒸氣改質之改質器，亦可為進行部分氧化改質、自身熱改質之改質器。改質器5之改質方法除根據煤油之特性而設以外，還根據汽油、石腦油、輕油、甲醇、乙醇、DME(二 甲醚)、利用生物物質之生物燃料等液體燃料之特性而設。 Further, the reformer 5 is not limited to a reformer that performs steam reforming, and may be a reformer that performs partial oxidation reforming and self-heat reforming. The reforming method of the reformer 5 is not only based on the characteristics of kerosene, but also based on gasoline, naphtha, light oil, methanol, ethanol, DME (two Methyl ether) is provided by the characteristics of liquid fuels such as biofuels such as biomass.

(第3實施形態) (Third embodiment)

以下參照圖9~圖12對第3實施形態之燃料電池系統1進行詳細說明。 Hereinafter, the fuel cell system 1 of the third embodiment will be described in detail with reference to Figs. 9 to 12 .

圖9係第3實施形態之燃料電池系統之一實施形態之構成圖。如圖9所示，燃料電池系統1包括：生成含有氫之改質氣體之改質裝置2；自供給至改質裝置2中之液體燃料中除去硫成分之脫硫裝置3；以及使用由改質裝置2生成之改質氣體進行發電之燃料電池堆疊4。燃料電池系統1例如係用作家庭用之電力供給源者，自能容易獲得且能獨立儲存之觀點考慮，使用煤油作為液體燃料。 Fig. 9 is a configuration diagram showing an embodiment of a fuel cell system according to a third embodiment. As shown in FIG. 9, the fuel cell system 1 includes: a reforming device 2 for generating a reformed gas containing hydrogen; and a desulfurizing device 3 for removing a sulfur component from the liquid fuel supplied to the reforming device 2; The reformed gas generated by the mass device 2 is used to generate a fuel cell stack 4 for power generation. The fuel cell system 1 is used, for example, as a power source for household use, and uses kerosene as a liquid fuel from the viewpoint of being easily available and capable of being independently stored.

改質裝置2具有對液體燃料進行水蒸氣改質而生成改質氣體之改質器5及對收容在改質器5內之改質觸媒進行加熱之燃燒器6。燃燒器6藉由加熱用於促進水蒸氣改質反應之改質觸媒，將使觸媒反應有效地發揮所需之熱供給於改質觸媒。在改質器5中，自脫硫裝置3導入之液體燃料氣化而成為原料氣體，利用改質觸媒促進原料氣體及水蒸氣(水)之間之水蒸氣改質反應，生成富氫之改質氣體。 The reforming device 2 includes a reformer 5 that reforms a liquid fuel by steam reforming to generate a reformed gas, and a combustor 6 that heats the reforming catalyst contained in the reformer 5. The burner 6 supplies the reforming catalyst by effectively heating the catalyst to effectively exert the required heat by heating the reforming catalyst for promoting the steam reforming reaction. In the reformer 5, the liquid fuel introduced from the desulfurization device 3 is vaporized to become a raw material gas, and the reforming catalyst is used to promote the steam reforming reaction between the raw material gas and the water vapor (water) to generate hydrogen-rich gas. Modified gas.

燃料電池堆疊4係多個電池單元堆積而構成之固體高分子型燃料電池堆疊，使用在改質裝置2得至之改質氣體進行發電。各電池單元具有陽極、陰極及配置在陽極與陰極之間之作為電解質之高分子離子交換膜。在各電池單元中，改質氣體被導入至陽極並且空氣被導入至陰極，從而進行電化學之發電反應。 The fuel cell stack 4 is a solid polymer fuel cell stack in which a plurality of battery cells are stacked, and the reformed gas obtained by the reforming device 2 is used for power generation. Each of the battery cells has an anode, a cathode, and a polymer ion exchange membrane as an electrolyte disposed between the anode and the cathode. In each of the battery cells, the reformed gas is introduced to the anode and the air is introduced to the cathode to perform an electrochemical power generation reaction.

圖10係圖9之燃料電池系統所具有之脫硫裝置之構成圖。如圖10所示，脫硫裝置3具有收容脫硫觸媒7a之脫硫器7，該脫硫觸媒7a用於自供給至改質器5中之液體燃料中除去硫成分。脫硫觸媒7a由加熱器(加熱機構)8加熱至特定溫度。在脫硫器7之上游側設有調節向脫硫器7內導入液體燃料之導入量之入口閥(液體燃料導入機構)9。並且，在 入口閥9之上游側設有將液體燃料加壓輸送至脫硫器7內之泵(液體燃料導入機構)11。另一方面，在脫硫器7之下游側設有調節來自脫硫器7內之液體燃料之導出量之出口閥(液體燃料導出機構)12。 Fig. 10 is a view showing the configuration of a desulfurization apparatus included in the fuel cell system of Fig. 9. As shown in Fig. 10, the desulfurization apparatus 3 has a desulfurizer 7 containing a desulfurization catalyst 7a for removing sulfur components from the liquid fuel supplied to the reformer 5. The desulfurization catalyst 7a is heated by a heater (heating mechanism) 8 to a specific temperature. An inlet valve (liquid fuel introduction means) 9 for adjusting the introduction amount of the liquid fuel into the desulfurizer 7 is provided on the upstream side of the desulfurizer 7. And, in On the upstream side of the inlet valve 9, a pump (liquid fuel introduction means) 11 for pressurizing the liquid fuel into the desulfurizer 7 is provided. On the other hand, an outlet valve (liquid fuel discharge mechanism) 12 for regulating the amount of liquid fuel from the desulfurizer 7 is provided on the downstream side of the desulfurizer 7.

又，在脫硫器7上設有測量脫硫器7內之液體燃料之溫度之溫度計(溫度測量機構)13。並且，在脫硫器7及入口閥9之間設有測量脫硫器7內之液體燃料之壓力之壓力計(壓力測量機構)14。控制部(控制機構)15根據由溫度計13測量之溫度及由壓力計14測量之壓力，對加熱器8、入口閥9、泵11及出口閥12進行控制。 Further, a thermometer (temperature measuring means) 13 for measuring the temperature of the liquid fuel in the desulfurizer 7 is provided in the desulfurizer 7. Further, a pressure gauge (pressure measuring means) 14 for measuring the pressure of the liquid fuel in the desulfurizer 7 is provided between the desulfurizer 7 and the inlet valve 9. The control unit (control means) 15 controls the heater 8, the inlet valve 9, the pump 11, and the outlet valve 12 based on the temperature measured by the thermometer 13 and the pressure measured by the pressure gauge 14.

如圖9所示，脫硫裝置3與供硫成分被除去之液體燃料流通之液體燃料流通管線16之一端相連接，液體燃料流通管線16之另一端與配置在脫硫裝置3上方之儲存容器19之側壁相連接。儲存容器19之底壁與液體燃料流通管線23、液體燃料流通管線25相連接，該液體燃料流通管線23上設有用於將儲存在儲存容器19內之下方之液體燃料導入至改質器5中之泵22，該液體燃料流通管線25上設有用於將該液體燃料導入至燃燒器6中之泵24。再者，燃燒器6與設有用於將空氣導入燃燒器6中之泵26之空氣流通管線27相連接。如此，藉由將液體燃料暫時儲存在儲存容器19中，可使泵22對改質器5之液體燃料之供給及泵24對燃燒器6之液體燃料之供給穩定化。 As shown in FIG. 9, the desulfurization device 3 is connected to one end of the liquid fuel circulation line 16 through which the liquid fuel from which the sulfur component is removed, and the other end of the liquid fuel circulation line 16 and the storage container disposed above the desulfurization device 3. The side walls of 19 are connected. The bottom wall of the storage container 19 is connected to the liquid fuel circulation line 23 and the liquid fuel circulation line 25, and the liquid fuel circulation line 23 is provided with a liquid fuel for being stored in the storage container 19 to be introduced into the reformer 5. The pump 22 is provided with a pump 24 for introducing the liquid fuel into the burner 6. Further, the burner 6 is connected to an air flow line 27 provided with a pump 26 for introducing air into the burner 6. Thus, by temporarily storing the liquid fuel in the storage container 19, the supply of the liquid fuel to the reformer 5 by the pump 22 and the supply of the liquid fuel to the burner 6 by the pump 24 can be stabilized.

在如上所述般構成之燃料電池系統1中，液體燃料首先被導入至脫硫裝置3之脫硫器7中，在高溫、高壓之狀態下，利用脫硫觸媒7a除去硫成分。自脫硫器7被導出之液體燃料經由液體燃料流通管線16而儲存至儲存容器19中。被儲存至儲存容器19中之液體燃料經由液體燃料流通管線23而導入至改質器5中。此時，液體燃料經由液體燃料流通管線25而導入至燃燒器6中，並且空氣經由空氣流通管線27而導入至燃燒器6中。藉此，在改質器5中，改質觸媒被進行燃燒之燃燒器6加熱，使用液體燃料而生成改質氣體。在改質器5中生成之改質氣體 被導入至燃料電池堆疊4中，在燃料電池堆疊4中，使用改質氣體進行發電。 In the fuel cell system 1 configured as described above, the liquid fuel is first introduced into the desulfurizer 7 of the desulfurization apparatus 3, and the sulfur component is removed by the desulfurization catalyst 7a under high temperature and high pressure. The liquid fuel derived from the desulfurizer 7 is stored in the storage container 19 via the liquid fuel circulation line 16. The liquid fuel stored in the storage container 19 is introduced into the reformer 5 via the liquid fuel circulation line 23. At this time, the liquid fuel is introduced into the combustor 6 via the liquid fuel circulation line 25, and the air is introduced into the combustor 6 via the air flow line 27. Thereby, in the reformer 5, the reforming catalyst is heated by the burner 6 that performs combustion, and the reformed gas is generated using the liquid fuel. Modified gas generated in the reformer 5 It is introduced into the fuel cell stack 4, and in the fuel cell stack 4, the reformed gas is used for power generation.

繼而，說明脫硫裝置3之動作。圖11係表示圖10之脫硫裝置之停止運轉時之溫度及壓力之間之關係之表，圖12係表示圖10之脫硫裝置之動作之流程圖。 Next, the operation of the desulfurization device 3 will be described. Fig. 11 is a table showing the relationship between temperature and pressure when the desulfurization apparatus of Fig. 10 is stopped, and Fig. 12 is a flow chart showing the operation of the desulfurization apparatus of Fig. 10.

如圖11所示，控制部15將停止時之各溫度範圍之脫硫器7內之壓力下限值(目標值)存儲作為資料表。壓力之下限值例如在150℃以上時為200kPa，在100℃~150℃時為100kPa。又，例如在100℃以下時為5kPa。比通常運轉時之溫度低之100℃(特定溫度)以下之壓力係設定為作為正壓(負壓以上)之特定壓力。 As shown in Fig. 11, the control unit 15 stores the pressure lower limit value (target value) in the desulfurizer 7 in each temperature range at the time of stop as a data table. The lower limit of the pressure is, for example, 200 kPa at 150 ° C or higher, and 100 kPa at 100 ° C to 150 ° C. Further, for example, it is 5 kPa at 100 ° C or lower. The pressure below 100 ° C (specific temperature) lower than the temperature during normal operation is set to a specific pressure as a positive pressure (negative pressure or higher).

如圖12所示，脫硫裝置3之停止動作開始時，為停止將液體燃料導入至脫硫器7內，控制部15使泵11停止並關閉入口閥9及出口閥12(步驟S11)，進而使加熱器8停止(步驟S12)。 As shown in FIG. 12, when the stop operation of the desulfurization device 3 is started, in order to stop the introduction of the liquid fuel into the desulfurizer 7, the control unit 15 stops the pump 11 and closes the inlet valve 9 and the outlet valve 12 (step S11). Further, the heater 8 is stopped (step S12).

步驟S12之處理後，控制部15對由壓力計14所測量之壓力、即脫硫器7內之液體燃料之壓力是否比壓力A(例如5kPa)高進行判斷(步驟S13)。於其結果為脫硫器7內之液體燃料之壓力比壓力A高之情形時，返回至步驟S13之判斷處理。另一方面，於脫硫器7內之液體燃料之壓力比壓力A低之情形時，為將液體燃料導入至脫硫器7內，控制部15使泵11動作並開啟入口閥9(步驟S14)。 After the process of step S12, the control unit 15 determines whether the pressure measured by the pressure gauge 14, that is, the pressure of the liquid fuel in the desulfurizer 7, is higher than the pressure A (for example, 5 kPa) (step S13). If the result is that the pressure of the liquid fuel in the desulfurizer 7 is higher than the pressure A, the process returns to the determination process of step S13. On the other hand, when the pressure of the liquid fuel in the desulfurizer 7 is lower than the pressure A, in order to introduce the liquid fuel into the desulfurizer 7, the control unit 15 operates the pump 11 and opens the inlet valve 9 (step S14). ).

步驟S14之處理後，控制部15對由壓力計14測量之壓力、即脫硫器7內之液體燃料之壓力是否比壓力B(例如40kPa)高進行判斷(步驟S15)。其結果為脫硫器7內之液體燃料之壓力比壓力B高之情形時，為停止將液體燃料導入至脫硫器7內，控制部15使泵11停止並關閉入口閥9(步驟S16)，返回至步驟S13之判斷處理。另一方面，在脫硫器7內之液體燃料壓力比壓力B高之情形時，返回至步驟S15之判斷處理。 After the process of step S14, the control unit 15 determines whether the pressure measured by the pressure gauge 14, that is, the pressure of the liquid fuel in the desulfurizer 7, is higher than the pressure B (for example, 40 kPa) (step S15). As a result, when the pressure of the liquid fuel in the desulfurizer 7 is higher than the pressure B, the control unit 15 stops the pump 11 and closes the inlet valve 9 (step S16) in order to stop the introduction of the liquid fuel into the desulfurizer 7. And it returns to the judgment process of step S13. On the other hand, when the liquid fuel pressure in the desulfurizer 7 is higher than the pressure B, the process returns to the determination process of step S15.

如上說明般，在燃料電池系統1之脫硫裝置3中，在由溫度計13測 量之溫度、即脫硫器7內之液體燃料之溫度為比通常運轉時之溫度低之特定溫度以下之情形時，控制部15對入口閥9、泵11及出口閥12進行控制，使得由壓力計14測量之壓力、即脫硫器7內之液體燃料之壓力達到作為正壓之特定壓力。因此，例如在停止運轉時，即使壓力隨著液體燃料之溫度之降低而降低，由於作為正壓之特定壓力被保持，因此可防止由壓力降低引起之例如液體燃料之氣化、脫硫器7之破損等對脫硫器7之不良影響。 As described above, in the desulfurization device 3 of the fuel cell system 1, it is measured by the thermometer 13 When the temperature of the amount, that is, the temperature of the liquid fuel in the desulfurizer 7 is lower than a specific temperature lower than the temperature during normal operation, the control unit 15 controls the inlet valve 9, the pump 11, and the outlet valve 12 so that The pressure measured by the pressure gauge 14, that is, the pressure of the liquid fuel in the desulfurizer 7, reaches a specific pressure as a positive pressure. Therefore, for example, when the operation is stopped, even if the pressure is lowered as the temperature of the liquid fuel is lowered, since the specific pressure as the positive pressure is maintained, for example, the vaporization of the liquid fuel caused by the pressure drop can be prevented, and the desulfurizer 7 can be prevented. The damage or the like has an adverse effect on the desulfurizer 7.

在使由壓力計14測量之壓力上升之情形時，控制部15使泵11動作並開啟入口閥9而使液體燃料之導入量增加，並且關閉出口閥12而使液體燃料之導出量減少。另一方面，在使由壓力計14測量之壓力降低之情形時，控制部15使泵11停止並關閉入口閥9而使液體燃料之導入量減少，並且開啟出口閥12而使液體燃料之導出量增加。藉此，可迅速且確實地使由壓力計14測量之壓力、即脫硫器7內之液體燃料之壓力上升或降低。又，所謂「關閉入口閥9(或出口閥12)」不僅係指完全關閉而流量為0之情形，亦包括未完全關閉而流量減少之情形。 When the pressure measured by the pressure gauge 14 is raised, the control unit 15 operates the pump 11 and opens the inlet valve 9 to increase the introduction amount of the liquid fuel, and closes the outlet valve 12 to reduce the amount of liquid fuel to be discharged. On the other hand, when the pressure measured by the pressure gauge 14 is lowered, the control portion 15 stops the pump 11 and closes the inlet valve 9 to reduce the introduction amount of the liquid fuel, and opens the outlet valve 12 to discharge the liquid fuel. The amount increases. Thereby, the pressure measured by the pressure gauge 14, that is, the pressure of the liquid fuel in the desulfurizer 7 can be quickly and surely increased or decreased. Further, the term "closing the inlet valve 9 (or the outlet valve 12)" means not only the case where the flow rate is zero when it is completely closed, but also the case where the flow rate is not completely closed and the flow rate is reduced.

本發明之第3側面不限定於上述實施形態。 The third aspect of the present invention is not limited to the above embodiment.

例如，燃料電池堆疊4不限於固體高分子型燃料電池堆疊，亦可為固體氧化物型燃料電池堆疊等。 For example, the fuel cell stack 4 is not limited to a solid polymer fuel cell stack, and may be a solid oxide fuel cell stack or the like.

又，改質器5不限於水蒸氣改質之改質器，亦可為部分氧化改質、自身熱改質之改質器。改質器5之改質方法除根據煤油之特性而設以外，還根據汽油、石腦油、輕油、甲醇、乙醇、DME(二甲醚)、利用生物物質之生物燃料等液體燃料之特性而設。 Moreover, the reformer 5 is not limited to a reformer that is modified by steam, and may be a reformer that is partially oxidized and modified by itself. The reforming method of the reformer 5 is based on the characteristics of kerosene, and is based on the characteristics of liquid fuels such as gasoline, naphtha, light oil, methanol, ethanol, DME (dimethyl ether), biofuels using biomass, and the like. And set.

(第4實施形態) (Fourth embodiment)

以下參照圖13及圖14對第4實施形態之燃料電池系統1進行詳細地說明。 The fuel cell system 1 of the fourth embodiment will be described in detail below with reference to Figs. 13 and 14 .

圖13係第4實施形態之燃料電池系統之實施形態之構成圖。如圖 13所示，燃料電池系統1包括：生成含有氫之改質氣體之改質裝置2；自供給至改質裝置2中之液體燃料中除去硫成分之脫硫裝置3；以及使用由改質裝置2生成之改質氣體進行發電之燃料電池堆疊4。燃料電池系統1例如係用作家庭用之電力供給源，自可容易獲得且可獨立儲存之觀點考慮，使用煤油作為液體燃料。 Fig. 13 is a configuration diagram of an embodiment of a fuel cell system according to a fourth embodiment. As shown As shown in FIG. 13, the fuel cell system 1 includes: a reforming device 2 for generating a reformed gas containing hydrogen; a desulfurizing device 3 for removing a sulfur component from the liquid fuel supplied to the reforming device 2; and a use of the reforming device 2 The generated modified gas is used to generate a fuel cell stack 4 for power generation. The fuel cell system 1 is used, for example, as a power supply source for household use, and kerosene is used as a liquid fuel from the viewpoint of being easily available and independently storageable.

改質裝置2具有對液體燃料進行水蒸氣改質而生成改質氣體之改質器5及對收容在改質器5內之改質觸媒進行加熱之燃燒器6。燃燒器6藉由加熱用於促進水蒸氣改質反應之改質觸媒，將使觸媒反應有效地發揮所需之熱供給於改質觸媒。在改質器5中，自脫硫裝置3導入之液體燃料氣化而成為原料氣體，利用改質觸媒促進原料氣體及水蒸氣(水)之間之水蒸氣改質反應，生成富氫之改質氣體。 The reforming device 2 includes a reformer 5 that reforms a liquid fuel by steam reforming to generate a reformed gas, and a combustor 6 that heats the reforming catalyst contained in the reformer 5. The burner 6 supplies the reforming catalyst by effectively heating the catalyst to effectively exert the required heat by heating the reforming catalyst for promoting the steam reforming reaction. In the reformer 5, the liquid fuel introduced from the desulfurization device 3 is vaporized to become a raw material gas, and the reforming catalyst is used to promote the steam reforming reaction between the raw material gas and the water vapor (water) to generate hydrogen-rich gas. Modified gas.

燃料電池堆疊4係多個電池單元堆積而構成之固體高分子型燃料電池堆疊，使用在改質裝置2獲得之改質氣體進行發電。各電池單元具有陽極、陰極及配置在陽極與陰極之間之作為電解質之高分子離子交換膜。在各電池單元中，改質氣體被導入至陽極並且空氣被導入至陰極，從而進行電化學之發電反應。 The fuel cell stack 4 is a solid polymer fuel cell stack in which a plurality of battery cells are stacked, and the reformed gas obtained by the reforming device 2 is used for power generation. Each of the battery cells has an anode, a cathode, and a polymer ion exchange membrane as an electrolyte disposed between the anode and the cathode. In each of the battery cells, the reformed gas is introduced to the anode and the air is introduced to the cathode to perform an electrochemical power generation reaction.

脫硫裝置3包括：自由泵7導入之液體燃料中除去硫成分之脫硫器8；以及儲存自脫硫器8排出之液體燃料及氣體(沼氣及氫氣等)之氣液分離容器9。為檢測氣體之量而在氣液分離容器9內設有檢測液體燃料之液面之浮動開關11。氣液分離容器9係配置在脫硫器8之上方，供液體燃料及氣體流通之液體燃料、氣體流通管線12之一端與脫硫器8之底壁相連接，另一端與氣液分離容器9之底壁相連接。藉此，可確實地將自脫硫器8排出之氣體導入至氣液分離容器9內。 The desulfurization apparatus 3 includes a desulfurizer 8 that removes a sulfur component from the liquid fuel introduced by the free pump 7, and a gas-liquid separation vessel 9 that stores the liquid fuel and gas (biogas, hydrogen, etc.) discharged from the desulfurizer 8. A float switch 11 for detecting the liquid level of the liquid fuel is provided in the gas-liquid separation container 9 for detecting the amount of gas. The gas-liquid separation container 9 is disposed above the desulfurizer 8, and one end of the liquid fuel and gas circulation line 12 through which the liquid fuel and the gas are circulated is connected to the bottom wall of the desulfurizer 8, and the other end is connected to the gas-liquid separation container 9 The bottom walls are connected. Thereby, the gas discharged from the desulfurizer 8 can be surely introduced into the gas-liquid separation container 9.

氣液分離容器9之頂壁與氣體排出管線13之一端相連接，該氣體排出管線13用於將儲存在氣液分離容器9內之上方之氣體自氣液分離容器9排出。氣體排出管線13之另一端與用於對改質器5之改質觸媒進 行加熱之燃燒器6相連接。在氣體排出管線13上設有開啟及關閉氣體之流通之電磁閥(開閉閥)14。電磁閥14與氣液分離容器9協同動作，構成用於自液體燃料中除去氣體之除氣器(degasser)D。並且，在氣體排出管線13之電磁閥14之下游側設有阻礙氣體流通之毛細管(節流機構)15。又，氣體排出管線13之毛細管15之下游側與設有用於將空氣導入至燃燒器6中之泵16之空氣流通管線17相連接。 The top wall of the gas-liquid separation container 9 is connected to one end of a gas discharge line 13 for discharging the gas stored above the gas-liquid separation container 9 from the gas-liquid separation container 9. The other end of the gas discharge line 13 and the modified catalyst for the reformer 5 The heated burners 6 are connected. A solenoid valve (opening and closing valve) 14 that opens and closes the flow of the gas is provided in the gas discharge line 13. The solenoid valve 14 cooperates with the gas-liquid separation container 9 to constitute a degasser D for removing gas from the liquid fuel. Further, a capillary tube (throttle mechanism) 15 that blocks the flow of the gas is provided on the downstream side of the electromagnetic valve 14 of the gas discharge line 13. Further, the downstream side of the capillary 15 of the gas discharge line 13 is connected to an air flow line 17 provided with a pump 16 for introducing air into the burner 6.

另一方面，氣液分離容器9之底壁與液體燃料排出管線18之一端相連接，該液體燃料排出管線18用於將儲存在氣液分離容器9內之下方之液體燃料自氣液分離容器9排出。液體燃料排出管線18之另一端與配置在氣液分離容器9之上方之儲存容器19之側壁相連接。在液體燃料排出管線18上設有阻礙液體燃料流通之毛細管21。 On the other hand, the bottom wall of the gas-liquid separation container 9 is connected to one end of a liquid fuel discharge line 18 for separating the liquid fuel stored in the gas-liquid separation container 9 from the gas-liquid separation container. 9 discharge. The other end of the liquid fuel discharge line 18 is connected to the side wall of the storage container 19 disposed above the gas-liquid separation container 9. A capillary 21 that blocks the flow of the liquid fuel is provided in the liquid fuel discharge line 18.

儲存容器19之底壁與液體燃料流通管線23、液體燃料流通管線25相連接，在該液體燃料流通管線23上設有用於將儲存在儲存容器19內之下方之液體燃料導入至改質器5中之泵22，在該液體燃料流通管線25上設有用於將該液體燃料導入至燃燒器6中之泵24。如此，藉由將液體燃料暫時儲存在儲存容器19中，可使泵22對改質器5之液體燃料之供給及泵24對燃燒器6之液體燃料之供給穩定化。 The bottom wall of the storage container 19 is connected to the liquid fuel circulation line 23 and the liquid fuel circulation line 25, and the liquid fuel circulation line 23 is provided with a liquid fuel for introducing the liquid fuel stored in the storage container 19 to the reformer 5 The pump 22 is provided with a pump 24 for introducing the liquid fuel into the burner 6 on the liquid fuel circulation line 25. Thus, by temporarily storing the liquid fuel in the storage container 19, the supply of the liquid fuel to the reformer 5 by the pump 22 and the supply of the liquid fuel to the burner 6 by the pump 24 can be stabilized.

在如上所述般構成之燃料電池系統1中，液體燃料首先被導入至脫硫器8中，在脫硫器8中，在高溫、高壓之狀態下藉由脫硫觸媒自液體燃料中除去硫成分。自脫硫器8排出之液體燃料及氣體被儲存於氣液分離容器9中，液體燃料經由液體燃料排出管線18、儲存容器19及液體燃料流通管線23而導入至改質器5中。此時，液體燃料經由液體燃料排出管線18、儲存容器19及液體燃料流通管線25而導入至燃燒器中，並且空氣經由空氣流通管線17而導入至燃燒器6中。藉此，在改質器5中，由燃燒之燃燒器6加熱改質觸媒，使用液體燃料而生成改質氣體。在改質器5中生成之改質氣體被導入至燃料電池堆疊4中，在燃 料電池堆疊4中，使用改質氣體進行發電。 In the fuel cell system 1 constructed as described above, the liquid fuel is first introduced into the desulfurizer 8, and in the desulfurizer 8, it is removed from the liquid fuel by the desulfurization catalyst in a state of high temperature and high pressure. Sulfur content. The liquid fuel and gas discharged from the desulfurizer 8 are stored in the gas-liquid separation container 9, and the liquid fuel is introduced into the reformer 5 via the liquid fuel discharge line 18, the storage container 19, and the liquid fuel circulation line 23. At this time, the liquid fuel is introduced into the combustor via the liquid fuel discharge line 18, the storage container 19, and the liquid fuel circulation line 25, and the air is introduced into the combustor 6 via the air flow line 17. Thereby, in the reformer 5, the reforming catalyst is heated by the burning burner 6, and the reformed gas is generated using the liquid fuel. The reformed gas generated in the reformer 5 is introduced into the fuel cell stack 4, and is burned In the battery stack 4, a reformed gas is used for power generation.

另一方面，被儲存在氣液分離容器9中之氣體經由氣體排出管線13而導入至燃燒器6中，與液體燃料一起被用作燃燒器6之燃料。如此，可將與液體燃料一起自脫硫器8排出之氣體有效地用作燃燒器6之燃料。再者，在電磁閥14關閉氣體之流通之情形時，在由浮動開關11檢測之氣液分離容器9內之氣體之量超過特定量時，電磁閥14分多次開啟氣體之流通。 On the other hand, the gas stored in the gas-liquid separation container 9 is introduced into the burner 6 via the gas discharge line 13, and is used as the fuel of the burner 6 together with the liquid fuel. Thus, the gas discharged from the desulfurizer 8 together with the liquid fuel can be effectively used as the fuel of the burner 6. Further, when the solenoid valve 14 closes the flow of the gas, when the amount of the gas in the gas-liquid separation container 9 detected by the float switch 11 exceeds a certain amount, the solenoid valve 14 opens the gas flow a plurality of times.

如以上說明般，在燃料電池系統1之脫硫裝置3中，與液體燃料一起自脫硫器8排出之氣體在氣液分離容器9中與液體燃料分離，經由氣體排出管線13自氣液分離容器9而排出。因此，可防止混入有氣體之液體燃料被供給至脫硫裝置3之後段(例如，泵22、24及改質器5等)。並且，在氣體排出管線13上，在開啟及關閉氣體之流通之電磁閥14之下游側設有阻礙氣體流通之毛細管15。因此，即使為將氣體經由氣體排出管線13自氣液分離容器9排出而由電磁閥14開啟氣體之流通，脫硫器8內之壓力之降低亦會被毛細管15抑制，從而被保持為高壓之狀態。因此，根據燃料電池系統1之脫硫裝置3，可防止對後段之不良影響，並可確實地自液體燃料中除去硫成分。 As described above, in the desulfurization device 3 of the fuel cell system 1, the gas discharged from the desulfurizer 8 together with the liquid fuel is separated from the liquid fuel in the gas-liquid separation container 9, and is separated from the gas and liquid via the gas discharge line 13. The container 9 is discharged. Therefore, it is possible to prevent the liquid fuel mixed with the gas from being supplied to the subsequent stage of the desulfurization device 3 (for example, the pumps 22, 24 and the reformer 5, etc.). Further, on the gas discharge line 13, a capillary 15 that blocks the flow of the gas is provided on the downstream side of the electromagnetic valve 14 that opens and closes the flow of the gas. Therefore, even if the gas is discharged from the gas-liquid separation container 9 via the gas discharge line 13 and the gas is opened by the solenoid valve 14, the pressure drop in the desulfurizer 8 is also suppressed by the capillary 15, thereby being maintained at a high pressure. status. Therefore, according to the desulfurization device 3 of the fuel cell system 1, the adverse effect on the rear stage can be prevented, and the sulfur component can be surely removed from the liquid fuel.

又，藉由設置在液體燃料排出管線18上之毛細管21，脫硫器8內之壓力降低亦被抑制而被保持為高壓之狀態。亦即，由於脫硫器8內之壓力被毛細管15、21維持為恆定，因此泵7可使用恆壓泵。 Further, by the capillary 21 provided in the liquid fuel discharge line 18, the pressure drop in the desulfurizer 8 is also suppressed and maintained in a high pressure state. That is, since the pressure in the desulfurizer 8 is maintained constant by the capillary tubes 15, 21, the pump 7 can use a constant pressure pump.

又，在電磁閥14關閉氣體之流通之情形時，在由浮動開關11檢測之氣液分離容器9內之氣體之量超過特定量時，電磁閥14分多次開啟氣體之流通。藉此，可更確實地抑制為將氣體經由氣體排出管線13自氣液分離容器9排出而由電磁閥14開啟氣體之流通時之脫硫器8內之壓力降低。 Further, when the solenoid valve 14 closes the flow of the gas, when the amount of the gas in the gas-liquid separation container 9 detected by the float switch 11 exceeds a certain amount, the solenoid valve 14 opens the gas flow a plurality of times. Thereby, the pressure drop in the desulfurizer 8 when the gas is discharged from the gas-liquid separation container 9 through the gas discharge line 13 and the gas is opened by the electromagnetic valve 14 can be more reliably suppressed.

圖14係表示圖13之燃料電池系統中之浮動開關、電磁閥及脫硫器 之壓力之關係之圖表。如圖14所示，浮動開關11處於ON期間，即，氣液分離容器9內之氣體之量超過特定量期間(此處為15秒鐘)，以特定間隔(此處為5秒間隔)多次(此處為3次)短時間(此處為200m秒鐘)開啟電磁閥14。藉此，脫硫器8之入口及出口之壓力僅產生少許之壓力降低(此處為10~20kPa之壓力降低)，而被維持為高壓。 Figure 14 is a diagram showing the floating switch, solenoid valve and desulfurizer in the fuel cell system of Figure 13 A chart of the relationship between stress. As shown in FIG. 14, the floating switch 11 is in the ON period, that is, the amount of gas in the gas-liquid separation container 9 exceeds a certain amount period (here, 15 seconds), at a specific interval (here, 5 second intervals). The solenoid valve 14 is opened for a short time (here, 3 times) for a short time (here, 200 m seconds). Thereby, the pressure at the inlet and outlet of the desulfurizer 8 causes only a slight pressure drop (here, the pressure is reduced by 10 to 20 kPa), and is maintained at a high pressure.

本發明之第4側面不限於上述實施形態。 The fourth aspect of the present invention is not limited to the above embodiment.

例如，燃料電池堆疊4不限於固體高分子型燃料電池堆疊，亦可為固體氧化物型燃料電池堆疊等。 For example, the fuel cell stack 4 is not limited to a solid polymer fuel cell stack, and may be a solid oxide fuel cell stack or the like.

又，改質器5不限於水蒸氣改質之改質器，亦可為部分氧化改質、自身熱改質之改質器。改質器5之改質方法除根據煤油之特性而設以外，還根據汽油、石腦油、輕油、甲醇、乙醇、DME(二甲醚)、利用生物物質之生物燃料等液體燃料之特性而設。 Moreover, the reformer 5 is not limited to a reformer that is modified by steam, and may be a reformer that is partially oxidized and modified by itself. The reforming method of the reformer 5 is based on the characteristics of kerosene, and is based on the characteristics of liquid fuels such as gasoline, naphtha, light oil, methanol, ethanol, DME (dimethyl ether), biofuels using biomass, and the like. And set.

又，氣體排出管線13上之阻礙氣體流通之節流機構、液體燃料排出管線18上之阻礙液體燃料流通之節流機構不限於毛細管15、21，亦可利用節流孔、針型閥等。 Further, the throttle mechanism that blocks the flow of the gas in the gas discharge line 13 and the throttle mechanism that blocks the flow of the liquid fuel in the liquid fuel discharge line 18 are not limited to the capillary tubes 15, 21, and an orifice, a needle valve, or the like may be used.

(第5實施形態) (Fifth Embodiment)

以下參照圖15~圖21對第5實施形態之燃料電池系統1進行詳細說明。 Hereinafter, the fuel cell system 1 of the fifth embodiment will be described in detail with reference to Figs. 15 to 21 .

如圖15所示，燃料電池系統1包括：自供給之原燃料中除去硫成分之脫硫裝置2；對由脫硫裝置2除去了硫成分之液體燃料進行改質而生成改質氣體之改質裝置3；以及使用由改質裝置3生成之改質氣體進行發電之燃料電池堆疊4。燃料電池系統1例如係用作家庭用之電力供給源，自可容易獲得且能獨立儲存之觀點考慮，使用煤油作為原燃料。 As shown in FIG. 15, the fuel cell system 1 includes a desulfurization device 2 for removing a sulfur component from a raw fuel to be supplied, and a modification of a liquid fuel obtained by removing the sulfur component from the desulfurization device 2 to generate a reformed gas. The mass device 3; and the fuel cell stack 4 for generating electricity using the reformed gas generated by the reforming device 3. The fuel cell system 1 is used, for example, as a power supply source for household use, and kerosene is used as a raw material from the viewpoint of being easily available and capable of being independently stored.

改質裝置3具有對液體燃料進行水蒸氣改質而生成富氫之改質氣體之改質器5及對收容在改質器5內之改質觸媒進行加熱之燃燒器6。 燃燒器6藉由加熱用於促進水蒸氣改質反應之改質觸媒，將使觸媒反應有效地發揮所需之熱供給於改質觸媒。燃燒器6之燃料主要係原燃料及氧。因此，燃燒器6與用於供給原燃料之燃料管線25及與用於將空氣導入至燃燒器6中之鼓風機16相連結之空氣流通管線17相連接。在改質器5中，經脫硫裝置2脫硫之液體燃料氣化而成為原料氣體，藉由改質觸媒促進原料氣體及水蒸氣(水)之間之水蒸氣改質反應，生成富氫之改質氣體。 The reforming device 3 includes a reformer 5 that reforms a liquid fuel by steam reforming to generate a hydrogen-rich reformed gas, and a burner 6 that heats the reforming catalyst contained in the reformer 5. The burner 6 supplies the reforming catalyst by effectively heating the catalyst to effectively exert the required heat by heating the reforming catalyst for promoting the steam reforming reaction. The fuel of the burner 6 is mainly raw fuel and oxygen. Therefore, the burner 6 is connected to the fuel line 25 for supplying the raw fuel and the air circulation line 17 connected to the blower 16 for introducing the air into the burner 6. In the reformer 5, the liquid fuel desulfurized by the desulfurization device 2 is vaporized to become a material gas, and the reforming catalyst promotes the water vapor reforming reaction between the raw material gas and the water vapor (water) to generate a rich gas. Hydrogen reforming gas.

燃料電池堆疊4係多個電池單元堆積而構成之固體高分子型燃料電池堆疊，使用在改質裝置3獲得之改質氣體進行發電。各電池單元具有陽極、陰極及配置在陽極與陰極之間之作為電解質之高分子離子交換膜。在各電池單元中，改質氣體被導入至陽極並且空氣被導入至陰極，從而進行電化學之發電反應。 The fuel cell stack 4 is a solid polymer fuel cell stack in which a plurality of battery cells are stacked, and the reformed gas obtained by the reforming device 3 is used for power generation. Each of the battery cells has an anode, a cathode, and a polymer ion exchange membrane as an electrolyte disposed between the anode and the cathode. In each of the battery cells, the reformed gas is introduced to the anode and the air is introduced to the cathode to perform an electrochemical power generation reaction.

脫硫裝置2包括：自由恆壓泵7導入之原燃料中除去硫成分之脫硫器8；以及用於分離自脫硫器8排出之液體燃料及氣體(沼氣及氫氣等)之氣液分離容器9。原燃料包含大約80ppm以下之硫及硫化物等硫成分。脫硫器8自原燃料中除去硫成分，生成硫濃度為大約50ppb以下之液體燃料。脫硫器8內藉由後述之構成而保持為高壓狀態，在高壓狀態下進行脫硫反應。 The desulfurization device 2 includes: a desulfurizer 8 for removing sulfur components from the raw fuel introduced by the free constant pressure pump 7; and a gas-liquid separation for separating the liquid fuel and the gas (biogas, hydrogen, etc.) discharged from the desulfurizer 8 Container 9. The raw fuel contains sulfur components such as sulfur and sulfides of about 80 ppm or less. The desulfurizer 8 removes the sulfur component from the raw fuel to produce a liquid fuel having a sulfur concentration of about 50 ppb or less. The desulfurizer 8 is maintained in a high pressure state by a configuration described later, and the desulfurization reaction is performed in a high pressure state.

為檢測氣體之量而在氣液分離容器9內設置檢測液體燃料之液面之浮動開關11。氣液分離容器9被配置在脫硫器8之上方，供液體燃料及氣體流通之液體燃料、氣體流通管線12之一端與脫硫器8之底壁相連接，另一端與氣液分離容器9之底壁相連接。藉此，可確實地將自脫硫器8排出之氣體導入至氣液分離容器9內。該氣液分離容器9之容積係100cc左右。再者，雖未圖示，但為除去由脫硫器8除去硫成分之液體燃料中所包含之脫硫觸媒，在液體燃料、氣體流通管線12上設置過濾器。在第5實施形態中，例如，可使用網眼為0.026mm左右之 過濾器。 A float switch 11 for detecting the liquid level of the liquid fuel is provided in the gas-liquid separation container 9 for detecting the amount of gas. The gas-liquid separation container 9 is disposed above the desulfurizer 8, and one end of the liquid fuel and gas circulation line 12 through which the liquid fuel and the gas are circulated is connected to the bottom wall of the desulfurizer 8, and the other end is connected to the gas-liquid separation container 9 The bottom walls are connected. Thereby, the gas discharged from the desulfurizer 8 can be surely introduced into the gas-liquid separation container 9. The volume of the gas-liquid separation container 9 is about 100 cc. Further, although not shown, a filter is provided in the liquid fuel and gas flow line 12 in order to remove the desulfurization catalyst contained in the liquid fuel from which the sulfur component is removed by the desulfurizer 8. In the fifth embodiment, for example, the mesh can be used to be about 0.026 mm. filter.

氣液分離容器9之頂壁與氣體排出管線13之一端相連接，該氣體排出管線13用於將儲存在氣液分離容器9內之上方之氣體自氣液分離容器9排出。在氣體排出管線13上設有開啟及關閉氣體之流通之電磁閥14。電磁閥14與氣液分離容器9協同動作，構成自液體燃料中除去氣體之除氣器D。並且，在氣體排出管線13上之電磁閥14之下游側設有阻礙氣體流通之毛細管15。因此，即使為將氣體經由氣體排出管線自氣液分離容器排出而由電磁閥14開啟氣體之流通，脫硫器8及氣液分離容器9內之壓力之降低亦會被毛細管15抑制。又，氣體排出管線13上之毛細管15之下游側與空氣流通管線17相連接。 The top wall of the gas-liquid separation container 9 is connected to one end of a gas discharge line 13 for discharging the gas stored above the gas-liquid separation container 9 from the gas-liquid separation container 9. A solenoid valve 14 that opens and closes the flow of the gas is provided in the gas discharge line 13. The solenoid valve 14 cooperates with the gas-liquid separation container 9 to constitute a deaerator D that removes gas from the liquid fuel. Further, a capillary 15 that blocks the flow of the gas is provided on the downstream side of the electromagnetic valve 14 on the gas discharge line 13. Therefore, even if the gas is discharged from the gas-liquid separation container through the gas discharge line and the gas is opened by the electromagnetic valve 14, the pressure drop in the desulfurizer 8 and the gas-liquid separation container 9 is suppressed by the capillary 15. Further, the downstream side of the capillary 15 on the gas discharge line 13 is connected to the air flow line 17.

另一方面，氣液分離容器9之底壁與液體燃料排出管線18之一端相連接，該液體燃料排出管線18用於將儲存在氣液分離容器9內之下方之液體燃料自氣液分離容器9排出。液體燃料排出管線18之另一端與配置在氣液分離容器9之上方之儲存容器19之底壁相連接。在該液體燃料排出管線18上設有阻礙液體燃料流通之毛細管21。 On the other hand, the bottom wall of the gas-liquid separation container 9 is connected to one end of a liquid fuel discharge line 18 for separating the liquid fuel stored in the gas-liquid separation container 9 from the gas-liquid separation container. 9 discharge. The other end of the liquid fuel discharge line 18 is connected to the bottom wall of the storage container 19 disposed above the gas-liquid separation container 9. A capillary 21 that blocks the flow of the liquid fuel is provided in the liquid fuel discharge line 18.

此處，毛細管21係將極細管捲繞成螺旋狀而成者。毛細管21在脫硫器8之下游側對液體燃料之流量進行節流，因此可使脫硫器8內之流量為低流量。另一方面，由恆壓泵7向脫硫器8內加壓輸送液體燃料，因此脫硫器8內被加壓，從而在高壓下進行脫硫反應。例如，在1kW之燃料電池系統之情形時，毛細管21之內徑及被捲繞時之直徑係設定為液體燃料(液體燃料)之流量為10g/min以下，並且自恆壓泵7至毛細管21之流路內壓力為大於0.1MPa且為1.0MPa以下之高壓。具體而言，較好的是毛細管21之內徑為0.1mm~0.5mm左右，較好的是被捲繞成螺旋之直徑為10mm~100mm左右。 Here, the capillary 21 is obtained by winding a very thin tube into a spiral shape. The capillary 21 throttles the flow rate of the liquid fuel on the downstream side of the desulfurizer 8, so that the flow rate in the desulfurizer 8 can be made low. On the other hand, the liquid fuel is pressurized and supplied to the desulfurizer 8 by the constant pressure pump 7, so that the inside of the desulfurizer 8 is pressurized to perform the desulfurization reaction under high pressure. For example, in the case of a 1 kW fuel cell system, the inner diameter of the capillary 21 and the diameter at the time of winding are set to a flow rate of liquid fuel (liquid fuel) of 10 g/min or less, and from the constant pressure pump 7 to the capillary 21 The pressure in the flow path is a high pressure of more than 0.1 MPa and 1.0 MPa or less. Specifically, it is preferable that the inner diameter of the capillary 21 is about 0.1 mm to 0.5 mm, and it is preferable that the diameter of the spiral is about 10 mm to 100 mm.

如上所述，在液體燃料、氣體流通管線12上設有過濾器，但粒徑比網眼小之脫硫觸媒會通過過濾器，因此在毛細管21之內徑未達0.1 mm時，存在毛細管21容易被脫硫觸媒堵塞之傾向。另一方面，當毛細管21之內徑超過0.5mm時，存在難以以低流量輸送液體燃料之傾向。再者，可根據毛細管21被捲繞時之直徑之大小而調整壓損。 As described above, a filter is provided on the liquid fuel and gas circulation line 12, but the desulfurization catalyst having a smaller particle size than the mesh passes through the filter, so that the inner diameter of the capillary 21 is less than 0.1. In the case of mm, there is a tendency that the capillary 21 is easily clogged by the desulfurization catalyst. On the other hand, when the inner diameter of the capillary 21 exceeds 0.5 mm, there is a tendency that it is difficult to transport the liquid fuel at a low flow rate. Further, the pressure loss can be adjusted according to the diameter of the capillary 21 when it is wound.

在液體燃料排出管線18上之毛細管21之下游側設有流量計26。流量計26測量自毛細管21流出之液體燃料之流量。即，流量計26測量由脫硫器8內之脫硫反應生成之液體燃料之生成速度。該流量計26係設置在氣液分離容器9之下游側，因此測量的是氣體被分離後而流入之液體燃料之流量，可穩定地測量流量。 A flow meter 26 is provided on the downstream side of the capillary 21 on the liquid fuel discharge line 18. The flow meter 26 measures the flow rate of the liquid fuel flowing out of the capillary 21. That is, the flow meter 26 measures the rate of generation of the liquid fuel generated by the desulfurization reaction in the desulfurizer 8. The flow meter 26 is disposed on the downstream side of the gas-liquid separation container 9, so that the flow rate of the liquid fuel into which the gas is separated after the gas is separated is measured, and the flow rate can be stably measured.

脫硫裝置2更具有與液體燃料排出管線18相連結並配置在流量計26之下游側之儲油槽19。儲油槽19之頂壁與液體燃料流通管線23相連接，在該液體燃料流通管線23上設有用於將儲存在儲油槽19內之液體燃料輸出至改質器5中之輸出泵24。儲油槽19之頂壁還與用於將儲存在儲油槽19內之上方之氣體排出之氣體排出管線27相連接。 The desulfurization device 2 further has an oil reservoir 19 connected to the liquid fuel discharge line 18 and disposed on the downstream side of the flow meter 26. The top wall of the sump 19 is connected to a liquid fuel circulation line 23, and an output pump 24 for discharging the liquid fuel stored in the sump 19 to the reformer 5 is provided in the liquid fuel circulation line 23. The top wall of the sump 19 is also connected to a gas discharge line 27 for discharging the gas stored above the sump 19.

繼而，參照圖16及圖17，對儲油槽19進行詳細說明。儲油槽19係由頂壁19a、底壁19b、側壁19c構成之空心長方體狀之容器，容積係200cc左右。在儲油槽19上連結有流入管31，該流入管31在液體燃料排出管線18上將毛細管21與儲油槽19連結起來。流入管31貫穿底壁19b，流入管31之位於儲油槽19內之流入口31a朝上方開口。自該流入口31a向儲油槽19內流入有高壓之液體燃料。 Next, the oil reservoir 19 will be described in detail with reference to Figs. 16 and 17 . The oil storage tank 19 is a hollow rectangular parallelepiped container composed of a top wall 19a, a bottom wall 19b, and a side wall 19c, and has a volume of about 200 cc. An inflow pipe 31 is connected to the oil reservoir 19, and the inflow pipe 31 connects the capillary 21 and the oil reservoir 19 to the liquid fuel discharge line 18. The inflow pipe 31 penetrates the bottom wall 19b, and the inflow port 31a of the inflow pipe 31 located in the oil reservoir 19 opens upward. High-pressure liquid fuel flows into the oil reservoir 19 from the inlet 31a.

在儲油槽19之頂壁19a上設有排氣孔32，構成氣體排出管線27之排氣管33之一端***在排氣孔32中。該排氣管33之另一端朝大氣開放，因此儲油槽19內之壓力被保持為大氣壓，自流入之液體燃料中分離出包含於該液體燃料中之氣體。在儲油槽19內自液體燃料中分離出之氣體自排氣孔32流入排氣管33，並自排氣管33之另一端而排出。排氣管33之另一端係配置在鼓風機16之吸入口附近，因此氣體被鼓風機16吸入，利用為燃燒器6之燃燒燃料。 An exhaust hole 32 is provided in the top wall 19a of the oil reservoir 19, and one end of the exhaust pipe 33 constituting the gas discharge line 27 is inserted into the exhaust hole 32. The other end of the exhaust pipe 33 is open to the atmosphere, so that the pressure in the oil reservoir 19 is maintained at atmospheric pressure, and the gas contained in the liquid fuel is separated from the inflowing liquid fuel. The gas separated from the liquid fuel in the oil reservoir 19 flows into the exhaust pipe 33 from the exhaust hole 32, and is discharged from the other end of the exhaust pipe 33. The other end of the exhaust pipe 33 is disposed near the suction port of the blower 16, so that the gas is sucked by the blower 16 and used as the combustion fuel of the burner 6.

在儲油槽19中設有將輸出泵24及儲油槽19連結起來並構成液體燃料流通管線23之一部分之流出管34。該輸出泵24係常壓泵，例如係排出壓力為100kPa左右之泵。流出管34貫穿頂壁19a地***至儲油槽19中，流出管34之位於儲油槽19內之流出口34a朝下方開口。藉由輸出泵24之動作，儲油槽19內之液體燃料經由流出管34而向改質器5內送出。 The oil reservoir 19 is provided with an outflow pipe 34 that connects the output pump 24 and the oil reservoir 19 to form a part of the liquid fuel circulation line 23. The output pump 24 is a normal pressure pump, for example, a pump having a discharge pressure of about 100 kPa. The outflow pipe 34 is inserted into the oil reservoir 19 through the top wall 19a, and the outflow pipe 34a of the outflow pipe 34 located in the oil reservoir 19 opens downward. The liquid fuel in the oil reservoir (19) is sent to the reformer (5) via the outflow pipe (34) by the operation of the output pump (24).

儲油槽19內之液體燃料之控制水位S由浮子閥35進行控制。浮子閥35之安裝在臂之一端上之浮子36浮在液面上，在液面比控制水位S低之情形時，如圖16所示，液體燃料自流入管31之流入口31a流入至儲油槽19內。當液面達到水位S時，如圖17所示，安裝在臂之另一端上之塞子(tap)37嵌入至流入管31流入口31a內，流入管31內之流路被封閉。 The control water level S of the liquid fuel in the oil reservoir 19 is controlled by the float valve 35. The float 36 of the float valve 35 mounted on one end of the arm floats on the liquid surface. When the liquid level is lower than the control water level S, as shown in Fig. 16, the liquid fuel flows into the reservoir 31a from the inlet 31a of the inflow pipe 31. Inside the oil tank 19. When the liquid level reaches the water level S, as shown in Fig. 17, a tap 37 attached to the other end of the arm is fitted into the inflow port 31a of the inflow pipe 31, and the flow path in the inflow pipe 31 is closed.

流入至儲油槽19內之液體燃料中混入有脫硫器8內之脫硫觸媒之觸媒片38。藉由將液體燃料儲存在儲油槽19內，該脫硫觸媒之觸媒片38在儲油槽19內下沉，從而蓄積在儲油槽19之下部。即，儲油槽19之下部起到蓄積脫硫觸媒之觸媒片38之觸媒片儲存部39之作用。該脫硫觸媒之觸媒片38會對後段之設備帶來不良影響，因此為使其不自流出管34流出，流出口34a係位於觸媒片儲存部39之上方。又，為使自流入管31流入之液體燃料不會捲起脫硫觸媒之觸媒片38，流入口31a係位於觸媒片儲存部39之上方。 The liquid fuel that has flowed into the oil storage tank 19 is mixed with the catalytic sheet 38 of the desulfurization catalyst in the desulfurizer 8. By storing the liquid fuel in the oil reservoir 19, the catalyst sheet 38 of the desulfurization catalyst sinks in the oil reservoir 19 to accumulate in the lower portion of the oil reservoir 19. That is, the lower portion of the oil reservoir 19 functions as a catalyst sheet storage portion 39 for accumulating the catalyst sheet 38 of the desulfurization catalyst. The catalyst sheet 38 of the desulfurization catalyst adversely affects the equipment of the latter stage. Therefore, the outlet port 34a is located above the catalyst sheet storage portion 39 so as not to flow out of the outflow pipe 34. Further, in order to prevent the liquid fuel flowing from the inflow pipe 31 from rolling up the catalyst sheet 38 of the desulfurization catalyst, the inflow port 31a is located above the catalyst sheet storage portion 39.

為將蓄積在該觸媒片儲存部39中之脫硫觸媒之觸媒片38自儲油槽19排出，儲油槽19之底壁與排出管40相連結。在排出管40上介設有電磁閥41，藉由開啟電磁閥41可簡便地將在電磁閥41被關閉之期間蓄積在觸媒片儲存部39中之觸媒片38排出。 In order to discharge the catalyst sheet 38 of the desulfurization catalyst accumulated in the catalyst sheet storage portion 39 from the oil storage tank 19, the bottom wall of the oil reservoir 19 is connected to the discharge pipe 40. The electromagnetic valve 41 is interposed in the discharge pipe 40, and the catalyst piece 38 accumulated in the catalyst sheet storage portion 39 during the period in which the electromagnetic valve 41 is closed can be easily discharged by opening the electromagnetic valve 41.

在如上所述般構成之燃料電池系統1中，原燃料首先被導入至脫硫器8中，在脫硫器8中，在高溫、高壓之狀態下藉由脫硫觸媒自液體 燃料中除去硫成分。自脫硫器8被排出之液體燃料及氣體藉由儲存在氣液分離容器9中而進行分離，液體燃料被導入至液體燃料排出管線18中。液體燃料之流量在液體燃料排出管線18中在毛細管21下游側由流量計26進行測量，液體燃料流入至儲油槽19內。高壓之液體燃料流入至被保持為常壓之儲油槽19內，而氣體自液體燃料中分離。然後，液體燃料被儲存在儲油槽19內之後，藉由輸出泵24經由液體燃料流通管線23而導入至改質器5中。又，氣體自儲油槽19內經由氣體排出管線27而排出，利用鼓風機16向燃燒器6供給，作為燃料使用。 In the fuel cell system 1 constructed as described above, the raw fuel is first introduced into the desulfurizer 8, and in the desulfurizer 8, the desulfurization catalyst is self-liquided in a state of high temperature and high pressure. The sulfur component is removed from the fuel. The liquid fuel and gas discharged from the desulfurizer 8 are separated by being stored in the gas-liquid separation container 9, and the liquid fuel is introduced into the liquid fuel discharge line 18. The flow rate of the liquid fuel is measured by the flow meter 26 on the downstream side of the capillary 21 in the liquid fuel discharge line 18, and the liquid fuel flows into the oil reservoir 19. The high pressure liquid fuel flows into the oil storage tank 19 which is maintained at normal pressure, and the gas is separated from the liquid fuel. Then, after the liquid fuel is stored in the oil storage tank 19, it is introduced into the reformer 5 via the liquid fuel circulation line 23 by the output pump 24. Further, the gas is discharged from the oil storage tank 19 through the gas discharge line 27, and is supplied to the burner 6 by the blower 16, and used as fuel.

另一方面，原燃料經由燃料管線25而導入至燃燒器6中，並且空氣主要經由空氣流通管線17而導入至燃燒器6中。藉此，在改質器5中，改質觸媒被進行燃燒之燃燒器6加熱，由液體燃料生成改質氣體。在改質器5中生成之改質氣體被導入至燃料電池堆疊4中，燃料電池堆疊4使用改質氣體進行發電。 On the other hand, the raw fuel is introduced into the combustor 6 via the fuel line 25, and the air is mainly introduced into the combustor 6 via the air flow line 17. Thereby, in the reformer 5, the reforming catalyst is heated by the burner 6 that performs combustion, and the reformed gas is generated from the liquid fuel. The reformed gas generated in the reformer 5 is introduced into the fuel cell stack 4, and the fuel cell stack 4 is used to generate electricity using the reformed gas.

另一方面，被儲存在氣液分離容器9內之氣體經由氣體排出管線13而導入至燃燒器6中，與液體燃料一起用作燃燒器6之燃料。再者，電磁閥14在封閉氣體之流通之情形時，在由浮動開關11檢測之氣液分離容器9內之氣體之量超過特定量時，電磁閥14分多次開啟氣體之流通。 On the other hand, the gas stored in the gas-liquid separation container 9 is introduced into the burner 6 via the gas discharge line 13, and serves as a fuel for the burner 6 together with the liquid fuel. Further, when the solenoid valve 14 is in the flow of the closed gas, when the amount of the gas in the gas-liquid separation container 9 detected by the float switch 11 exceeds a certain amount, the solenoid valve 14 opens the gas flow a plurality of times.

在儲油槽19中，液體燃料之液面達到控制水位S時，由浮子閥35封閉流入管31之流入口31a，液體燃料向儲油槽19內之流入停止。在液體燃料之液面比控制水位S低時，由浮子閥35開啟流入管31之流入口31a，液體燃料開始向儲油槽19內流入。 In the oil storage tank 19, when the liquid level of the liquid fuel reaches the control water level S, the inflow port 31a of the inflow pipe 31 is closed by the float valve 35, and the inflow of the liquid fuel into the oil storage tank 19 is stopped. When the liquid level of the liquid fuel is lower than the control water level S, the inlet port 31a of the inflow pipe 31 is opened by the float valve 35, and the liquid fuel starts to flow into the oil reservoir 19.

又，當觸媒片38蓄積在儲油槽19之觸媒片儲存部39中時，藉由開啟設置在排出管40上之電磁閥41，將觸媒片38自儲油槽19中排出。電磁閥41之開啟亦可設定為以特定之時間間隔進行。 Further, when the catalyst sheet 38 is accumulated in the catalyst sheet storage portion 39 of the oil reservoir 19, the catalyst sheet 38 is discharged from the oil reservoir 19 by opening the solenoid valve 41 provided on the discharge tube 40. The opening of the solenoid valve 41 can also be set to be performed at specific time intervals.

在如上說明之本實施形態之燃料電池系統1中，儲存液體燃料之 儲油槽19係配置在脫硫器8及改質器5之間，在該儲油槽19上設有朝大氣開放之排氣孔32。因此，原燃料在脫硫器8內在高壓下進行脫硫，經脫硫之液體燃料流入至儲油槽19內，並且包含於液體燃料中之氣體藉由排氣孔32而自儲油槽19內排出。由於包含於液體燃料中之氣體被排出，因此可增加在儲油槽19下游側之液體燃料之流量測量及流量控制之可靠性。因此，可確實地控制流入至改質器19內之液體燃料之流量，並可防止改質性能之降低。又，由於高壓狀態之液體燃料未流入至儲油槽19之下游側，因此無需與高壓相適應之設備，可提高儲油槽19之後段設備之耐久性，從而可實現低成本。 In the fuel cell system 1 of the present embodiment as described above, the liquid fuel is stored. The oil storage tank 19 is disposed between the desulfurizer 8 and the reformer 5, and the oil storage tank 19 is provided with an exhaust hole 32 that opens to the atmosphere. Therefore, the raw fuel is desulfurized in the desulfurizer 8 under high pressure, the desulfurized liquid fuel flows into the oil storage tank 19, and the gas contained in the liquid fuel is discharged from the oil storage tank 19 through the exhaust hole 32. . Since the gas contained in the liquid fuel is discharged, the reliability of the flow rate measurement and the flow rate control of the liquid fuel on the downstream side of the oil reservoir 19 can be increased. Therefore, the flow rate of the liquid fuel flowing into the reformer 19 can be surely controlled, and the deterioration of the reform performance can be prevented. Further, since the liquid fuel in the high pressure state does not flow to the downstream side of the oil storage tank 19, the equipment suitable for the high pressure is not required, and the durability of the equipment in the subsequent stage of the oil storage tank 19 can be improved, thereby achieving low cost.

又，第5實施形態之燃料電池系統1包括：以恆壓將原燃料加壓輸送至脫硫器8內之恆壓泵7；以及配置在脫硫器8之下游側且配置在儲油槽19之上游側之毛細管21。因此，原燃料以恆壓流入至脫硫器8內，另一方面，自脫硫器8之流出量受到節流。因此，不使用高價之泵便可使脫硫器內之壓力比大氣壓高，而且可將原燃料(液體燃料)之流量保持為較低。 Further, the fuel cell system 1 of the fifth embodiment includes a constant pressure pump 7 that pressurizes the raw fuel to the desulfurizer 8 at a constant pressure, and is disposed downstream of the desulfurizer 8 and disposed in the oil reservoir 19 The capillary 21 on the upstream side. Therefore, the raw fuel flows into the desulfurizer 8 at a constant pressure, and on the other hand, the outflow amount from the desulfurizer 8 is throttled. Therefore, the pressure in the desulfurizer can be made higher than atmospheric pressure without using a high-priced pump, and the flow rate of the raw fuel (liquid fuel) can be kept low.

又，在第5實施形態之燃料電池系統1中，與液體燃料一起自脫硫器8排出之氣體在氣液分離容器9中與液體燃料分離，並經由氣體排出管線13而自氣液分離容器9排出。在氣體排出管線13上，在開啟及關閉氣體流通之電磁閥14之下游側設有阻礙氣體流通之毛細管15。因此，即使為將氣體經由氣體排出管線13自氣液分離容器9排出而由電磁閥14開啟氣體之流通，脫硫器8內之壓力之降低亦會被毛細管15抑制。因此，可將脫硫器8內之壓力保持為高壓，可自原燃料中確實地除去硫成分。另一方面，液體燃料經由液體燃料排出管線18流入至儲油槽19內。由於在液體燃料排出管線18上設有流量計26，因此可穩定地測量與氣體分離之液體燃料之流量。 Further, in the fuel cell system 1 of the fifth embodiment, the gas discharged from the desulfurizer 8 together with the liquid fuel is separated from the liquid fuel in the gas-liquid separation container 9, and is separated from the gas-liquid separation tank via the gas discharge line 13. 9 discharge. On the gas discharge line 13, a capillary 15 for blocking the flow of the gas is provided on the downstream side of the electromagnetic valve 14 for opening and closing the gas. Therefore, even if the gas is discharged from the gas-liquid separation container 9 through the gas discharge line 13 and the gas is opened by the electromagnetic valve 14, the pressure drop in the desulfurizer 8 is also suppressed by the capillary 15. Therefore, the pressure in the desulfurizer 8 can be maintained at a high pressure, and the sulfur component can be surely removed from the raw fuel. On the other hand, the liquid fuel flows into the oil reservoir 19 via the liquid fuel discharge line 18. Since the flow meter 26 is provided on the liquid fuel discharge line 18, the flow rate of the liquid fuel separated from the gas can be stably measured.

又，在第5實施形態之燃料電池系統1中，可將與液體燃料一起自 脫硫器8流出之用於脫硫之觸媒片38蓄積在位於儲油槽19下部之觸媒片儲存部39內，使其不會流入後段之改質器5內。又，儲油槽19內之液體燃料之流入口31a及流出口34a位於觸媒片儲存部39之上方，因此，可抑制由於液體燃料之流入及流出而使蓄積在觸媒片儲存部39內之觸媒飛揚、自儲存槽19流出而流入至改質器5內。 Further, in the fuel cell system 1 of the fifth embodiment, it is possible to self-contain with the liquid fuel. The catalyst sheet 38 for desulfurization which flows out of the desulfurizer 8 is accumulated in the catalyst sheet storage portion 39 located at the lower portion of the oil reservoir 19 so as not to flow into the reformer 5 of the rear stage. Further, since the liquid fuel inlet port 31a and the outflow port 34a in the oil reservoir 19 are located above the catalyst sheet storage portion 39, accumulation of the liquid fuel into the catalyst sheet storage portion 39 can be suppressed. The catalyst flies, flows out of the storage tank 19, and flows into the reformer 5.

一般而言，在用泵將蓄積在容器內之液體抽出之情形時，該流出口為不吸入空氣而設置在容器之最下方。在第5實施形態之燃料電池系統1中，藉由將流出口34a設置在觸媒片儲存部39之上方，可抑制蓄積在觸媒片儲存部39內之觸媒飛揚、自儲存槽19流出而流入至改質器5內。 In general, when a liquid accumulated in a container is withdrawn by a pump, the outflow port is provided at the bottom of the container without inhaling air. In the fuel cell system 1 of the fifth embodiment, by providing the outflow port 34a above the catalyst sheet storage portion 39, the catalyst accumulated in the catalyst sheet storage portion 39 can be prevented from flying and flowing out of the storage tank 19. It flows into the reformer 5.

又，在第5實施形態之燃料電池系統1中，具有加熱改質器5之燃燒器6，該燃燒器6將自排氣孔32流出之流出氣體用作燃燒用之燃料。因此，可防止自排氣孔32流出之流出氣體流出至燃料電池系統1之周圍。又，由於使用流出氣體作為燃燒器6之燃料，所以可有助於節能。 Further, in the fuel cell system 1 of the fifth embodiment, the burner 6 of the heating reformer 5 is provided, and the burner 6 uses the outflow gas flowing out from the exhaust hole 32 as a fuel for combustion. Therefore, the outflow gas flowing out from the exhaust hole 32 can be prevented from flowing out to the periphery of the fuel cell system 1. Further, since the effluent gas is used as the fuel of the burner 6, it contributes to energy saving.

以上對本發明之第5側面之較佳實施形態進行詳細說明，但本發明之第5側面可進行各種變形。 The preferred embodiment of the fifth aspect of the present invention has been described in detail above, but the fifth aspect of the present invention can be variously modified.

如圖18所示，亦可不在燃料電池系統1中設置除氣器D、氣體排出管線13。作為燃料電池系統1a，亦可利用液體燃料、氣體流通管線12將脫硫器8與儲油槽19直接連接，並在液體燃料、氣體流通管線12上設有毛細管21。 As shown in FIG. 18, the deaerator D and the gas discharge line 13 may not be provided in the fuel cell system 1. As the fuel cell system 1a, the desulfurizer 8 and the oil reservoir 19 may be directly connected by a liquid fuel or a gas flow line 12, and a capillary 21 may be provided in the liquid fuel and gas flow line 12.

又，在第5實施形態中，為控制儲油槽19內之水位而設置浮子閥35，但不限於此。如圖19及圖20所示，替代浮子閥35，燃料電池系統1亦可包括：檢測儲油槽19內之液體燃料之液面達到低水位S1之低水位感測器51；檢測儲油槽19內之液體燃料之液面達到高水位S2之高水位感測器52；以及根據該低水位感測器51及高水位感測器52之輸出信 號進行控制之控制部53。作為該低水位感測器51及高水位感測器52，例如可使用浮動開關、電極式水位感測器、壓力式水位感測器等。 Further, in the fifth embodiment, the float valve 35 is provided to control the water level in the oil reservoir 19, but the invention is not limited thereto. As shown in FIG. 19 and FIG. 20, instead of the float valve 35, the fuel cell system 1 may further include: a low water level sensor 51 that detects that the liquid level of the liquid fuel in the oil storage tank 19 reaches a low water level S1; and detects the inside of the oil storage tank 19. The liquid level of the liquid fuel reaches the high water level sensor 52 of the high water level S2; and the output signal according to the low water level sensor 51 and the high water level sensor 52 The control unit 53 that controls the number. As the low water level sensor 51 and the high water level sensor 52, for example, a floating switch, an electrode type water level sensor, a pressure type water level sensor, or the like can be used.

於此情形時，在流入管31上設有電磁閥42，該電磁閥42之開閉由控制部53所具有之開閉控制部54進行控制。又，控制部53包括：對自低水位感測器51檢測到低水位S1至高水位感測器52檢測到高水位S2為止之時間進行測量之計時器55；根據計時器55之測量時間計算液體燃料之流量之計算部56；以及根據計算部56之計算結果進行恆壓泵7之控制之泵控制部57。 In this case, the inflow pipe 31 is provided with a solenoid valve 42, and the opening and closing of the solenoid valve 42 is controlled by the opening and closing control unit 54 of the control unit 53. Further, the control unit 53 includes a timer 55 for measuring the time from when the low water level sensor 51 detects the low water level S1 to when the high water level sensor 52 detects the high water level S2; and calculates the liquid based on the measurement time of the timer 55. The fuel flow rate calculation unit 56; and a pump control unit 57 that controls the constant pressure pump 7 based on the calculation result of the calculation unit 56.

當儲油槽19內之液體燃料之液面自比低水位S1高之狀態達到低水位S1時，藉由低水位感測器51檢測到液體燃料之液面達到低水位S1，自低水位感測器51向控制部53輸出電信號。自低水位感測器51輸出之電信號輸入至開閉控制部54時，開閉控制部54將電磁閥41自關閉狀態開啟，液體燃料開始流入至儲油槽19內。 When the liquid level of the liquid fuel in the oil storage tank 19 reaches the low water level S1 from the state higher than the low water level S1, the liquid level of the liquid fuel is detected by the low water level sensor 51 to reach the low water level S1, and the low water level is sensed. The device 51 outputs an electric signal to the control unit 53. When the electric signal output from the low water level sensor 51 is input to the opening and closing control unit 54, the opening and closing control unit 54 opens the electromagnetic valve 41 from the closed state, and the liquid fuel starts to flow into the oil storage tank 19.

當儲油槽19內之液體燃料之液面自比高水位S2低之狀態達到高水位S2時，藉由高水位感測器52檢測到液體燃料之液面達到高水位S2，自高水位感測器52向控制部53輸出電信號。自高水位感測器52輸出之電信號輸入至開閉控制部54時，開閉控制部54將電磁閥41自開啟狀態關閉，液體燃料向儲油槽19內之流入停止。 When the liquid level of the liquid fuel in the oil storage tank 19 reaches the high water level S2 from the state lower than the high water level S2, the liquid level of the liquid fuel is detected by the high water level sensor 52 to reach the high water level S2, and the high water level is sensed. The device 52 outputs an electric signal to the control unit 53. When the electric signal output from the high water level sensor 52 is input to the opening and closing control unit 54, the opening and closing control unit 54 closes the electromagnetic valve 41 from the open state, and the inflow of the liquid fuel into the oil storage tank 19 is stopped.

另一方面，自低水位感測器51輸出之電信號及自高水位感測器52輸出之電信號分別輸入至計時器55。計時器55對從輸入自低水位感測器51輸出之電信號至輸入自高水位感測器52輸出之電信號為止之時間進行測量，將表示該測量時間之電信號輸出至計算部56。計算部56輸入有來自計時器55之表示測量時間之電信號時，根據該測量時間算出液體燃料之流量。計算部56將表示所算出之流量之電信號輸出至泵控制部57。泵控制部57輸入有來自計算部56之表示流量之電信號時，根據該流量控制恆壓泵7之驅動。 On the other hand, the electric signal output from the low water level sensor 51 and the electric signal output from the high water level sensor 52 are input to the timer 55, respectively. The timer 55 measures the time from the input of the electric signal output from the low water level sensor 51 to the electric signal input from the high water level sensor 52, and outputs an electric signal indicating the measurement time to the calculation unit 56. When the calculation unit 56 inputs an electric signal indicating the measurement time from the timer 55, the flow rate of the liquid fuel is calculated based on the measurement time. The calculation unit 56 outputs an electric signal indicating the calculated flow rate to the pump control unit 57. When the pump control unit 57 receives an electric signal indicating the flow rate from the calculation unit 56, the pump control unit 57 controls the driving of the constant pressure pump 7 based on the flow rate.

於此情形時，水位感測器藉由計時器對檢測出低水位至檢測出高水位為止之時間進行測量，計算機構根據計時器之測量時間算出液體燃料之流量，因此無需另外設置流量計。藉此，可謀求更低成本化。 In this case, the water level sensor measures the time from the detection of the low water level to the detection of the high water level by the timer, and the calculation mechanism calculates the flow rate of the liquid fuel based on the measurement time of the timer, so there is no need to separately set the flow meter. Thereby, it is possible to achieve lower cost.

又，儲油槽19內之液體燃料之流入口31a及流出口34a位於低水位S1之下方，因此，可防止在液體燃料流入時液體燃料起泡，可防止在液體燃料流出時自水面下流出而捲入空氣。 Further, the liquid fuel inlet port 31a and the outflow port 34a in the oil reservoir 19 are located below the low water level S1, thereby preventing liquid fuel from foaming when the liquid fuel flows in, and preventing the liquid fuel from flowing out from the water surface when the liquid fuel flows out. Entrapped in the air.

再者，計算部56亦可根據自儲油槽19之流出管34流出之液體燃料之流量、輸出泵24之排出量等，算出液體燃料流入至儲油槽19內之流量。又，泵控制部57亦可根據計時器55之測量時間進行恆壓泵7之驅動控制。 Further, the calculating unit 56 may calculate the flow rate of the liquid fuel flowing into the oil storage tank 19 based on the flow rate of the liquid fuel flowing out from the outflow pipe 34 of the oil storage tank 19, the discharge amount of the output pump 24, and the like. Further, the pump control unit 57 can also perform drive control of the constant pressure pump 7 based on the measurement time of the timer 55.

又，如圖21所示，作為第5實施形態之燃料電池系統1之變形例，亦可在儲油槽19上連結溢流管43。該溢流管43之一端穿過儲油槽19之頂壁，一方開口43a配置在比儲油槽19內之水位S高之位置M，且朝下方開口。溢流管43沿著儲油槽19之側壁19c之外側配置，另一方開口43b位於儲油槽19之外側，且朝下方開口。因此，即使因浮子閥35之故障等某些原因而導致液體燃料充滿於儲油槽19內，液體燃料亦可利用溢流管43自儲油槽19排出。 Moreover, as shown in FIG. 21, as a modification of the fuel cell system 1 of the fifth embodiment, the overflow pipe 43 may be connected to the oil reservoir 19. One end of the overflow pipe 43 passes through the top wall of the oil reservoir 19, and one opening 43a is disposed at a position M higher than the water level S in the oil reservoir 19, and is opened downward. The overflow pipe 43 is disposed along the outer side of the side wall 19c of the oil sump 19, and the other opening 43b is located outside the oil sump 19 and opens downward. Therefore, even if the liquid fuel is filled in the oil reservoir 19 due to some cause such as the failure of the float valve 35, the liquid fuel can be discharged from the oil reservoir 19 by the overflow pipe 43.

在儲油槽19之下方配置有油盤44，自朝下方開口之溢流管43之另一方開口43b排出之液體燃料流入至油盤44內。當液體燃料流入至油盤44內時，藉由配置在油盤44之底面上之洩漏感測器45檢測出液體燃料漏出至油盤44內。於此情形時，控制裝置(未圖示)根據洩漏感測器45之檢測信號之輸入，進行使恆壓泵7之動作停止等之控制，從而可停止液體燃料之供給，使液體燃料之流出停止。 An oil pan 44 is disposed below the oil reservoir 19, and the liquid fuel discharged from the other opening 43b of the overflow pipe 43 opened downward flows into the oil pan 44. When the liquid fuel flows into the oil pan 44, the liquid fuel leaks out into the oil pan 44 by the leak sensor 45 disposed on the bottom surface of the oil pan 44. In this case, the control device (not shown) controls the operation of the constant pressure pump 7 to stop the operation of the constant pressure pump 7 based on the input of the detection signal of the leakage sensor 45, thereby stopping the supply of the liquid fuel and allowing the liquid fuel to flow out. stop.

再者，溢流管不限於上述方式，亦可形成為直線狀。於此情形時，溢流管係配置成自儲油槽19之底壁19b之開口***，一端配置在設定為儲油槽19內之滿水位之高度之位置，另一端位於儲油槽19外之 底壁19b之下方，且朝向油盤44開口。 Further, the overflow pipe is not limited to the above, and may be formed in a straight line shape. In this case, the overflow pipe is disposed to be inserted from the opening of the bottom wall 19b of the oil storage tank 19, one end is disposed at a position set to the height of the full water level in the oil storage tank 19, and the other end is located outside the oil storage tank 19. Below the bottom wall 19b, it opens toward the oil pan 44.

並且，第5實施形態之燃料電池系統可進行各種變形。燃料電池堆疊4不限於固體高分子型燃料電池堆疊，亦可為固體氧化物型燃料電池堆疊等。除煤油之外，還可利用汽油、石腦油、輕油、甲醇、乙醇、DME(二甲醚)、利用生物物質之生物燃料等液體燃料作為原燃料。又，改質器5不限於進行水蒸氣改質之改質器，亦可為進行部分氧化改質、自身熱改質之改質器。又，亦可使用定流量泵替代恆壓泵7。但自脫硫器8內之壓力管理之觀點考慮，較好的是使用恆壓泵7。 Further, the fuel cell system of the fifth embodiment can be variously modified. The fuel cell stack 4 is not limited to a solid polymer fuel cell stack, and may be a solid oxide fuel cell stack or the like. In addition to kerosene, liquid fuels such as gasoline, naphtha, light oil, methanol, ethanol, DME (dimethyl ether), and biofuels using biomass can be used as the raw fuel. Further, the reformer 5 is not limited to a reformer that performs steam reforming, and may be a reformer that performs partial oxidation reforming and self-heat reforming. Alternatively, a constant flow pump can be used instead of the constant pressure pump 7. However, it is preferable to use the constant pressure pump 7 from the viewpoint of pressure management in the desulfurizer 8.

(第6實施形態) (Sixth embodiment)

以下參照圖22及圖23對第6實施形態之燃料電池系統1進行詳細說明。 The fuel cell system 1 of the sixth embodiment will be described in detail below with reference to Figs. 22 and 23 .

如圖22所示，燃料電池系統1包括：生成含有氫之改質氣體之改質裝置2；自供給至改質裝置2中之液體燃料中除去硫成分之脫硫裝置3；以及使用由改質裝置2生成之改質氣體進行發電之燃料電池堆疊4。燃料電池系統1例如係用作家庭用之電力供給源，自可容易獲得且可獨立儲存之觀點考慮，使用煤油作為液體燃料。再者，由燃料電池系統1中之除燃料電池堆疊4以外之部分(改質裝置2、脫硫裝置3及後述之泵16、22、24)構成改質系統R。 As shown in FIG. 22, the fuel cell system 1 includes: a reforming device 2 for generating a reformed gas containing hydrogen; and a desulfurizing device 3 for removing a sulfur component from the liquid fuel supplied to the reforming device 2; The reformed gas generated by the mass device 2 is used to generate a fuel cell stack 4 for power generation. The fuel cell system 1 is used, for example, as a power supply source for household use, and kerosene is used as a liquid fuel from the viewpoint of being easily available and independently storageable. Further, the reforming system R is constituted by a portion other than the fuel cell stack 4 (the reforming device 2, the desulfurizing device 3, and the pumps 16, 22, and 24 to be described later) in the fuel cell system 1.

改質裝置2具有對液體燃料進行水蒸氣改質而生成改質氣體之改質器5及對收容在改質器5內之改質觸媒進行加熱之燃燒器6。燃燒器6藉由加熱用於促進水蒸氣改質反應之改質觸媒，將使觸媒反應有效地發揮所需之熱供給於改質觸媒。在改質器5中，自脫硫裝置3導入之液體燃料氣化而成為原料氣體，藉由改質觸媒促進原料氣體及水蒸氣(水)之間之水蒸氣改質反應，生成富氫之改質氣體。 The reforming device 2 includes a reformer 5 that reforms a liquid fuel by steam reforming to generate a reformed gas, and a combustor 6 that heats the reforming catalyst contained in the reformer 5. The burner 6 supplies the reforming catalyst by effectively heating the catalyst to effectively exert the required heat by heating the reforming catalyst for promoting the steam reforming reaction. In the reformer 5, the liquid fuel introduced from the desulfurization device 3 is vaporized to become a raw material gas, and the reforming catalyst promotes the steam reforming reaction between the raw material gas and the water vapor (water) to generate hydrogen-rich hydrogen. Modified gas.

燃料電池堆疊4係多個電池單元堆積而構成之固體高分子型燃料電池堆疊，使用在改質裝置2獲得之改質氣體進行發電。各電池單元 具有陽極、陰極及配置在陽極與陰極之間之作為電解質之高分子離子交換膜。在各電池單元中，改質氣體被導入至陽極並且空氣被導入至陰極，從而進行電化學之發電反應。 The fuel cell stack 4 is a solid polymer fuel cell stack in which a plurality of battery cells are stacked, and the reformed gas obtained by the reforming device 2 is used for power generation. Battery unit There is an anode, a cathode, and a polymer ion exchange membrane as an electrolyte disposed between the anode and the cathode. In each of the battery cells, the reformed gas is introduced to the anode and the air is introduced to the cathode to perform an electrochemical power generation reaction.

脫硫裝置3包括：自由恆壓泵7導入之液體燃料中除去硫成分之脫硫器8；以及對自脫硫器8排出之液體燃料及氣體(沼氣及氫氣等)進行儲存之氣液分離容器9。為檢測氣體之量而在氣液分離容器9內設有檢測液體燃料之液面之浮動開關11。氣液分離容器9係配置在脫硫器8之上方，供給液體燃料及氣體流通之液體燃料、氣體流通管線12之一端與脫硫器8之底壁相連接，另一端與氣液分離容器9之底壁相連接。藉此，可確實地將自脫硫器8排出之氣體導入至氣液分離容器9內。再者，雖未圖示，但為除去包含於由脫硫器8除去了硫成分之液體燃料中之脫硫觸媒，在液體燃料、氣體流通管線12上設有過濾器。在本實施形態中，例如可使用網眼為0.026mm左右之過濾器。 The desulfurization device 3 includes: a desulfurizer 8 for removing sulfur components from the liquid fuel introduced by the free constant pressure pump 7; and a gas-liquid separation for storing the liquid fuel and gas (biogas, hydrogen, etc.) discharged from the desulfurizer 8 Container 9. A float switch 11 for detecting the liquid level of the liquid fuel is provided in the gas-liquid separation container 9 for detecting the amount of gas. The gas-liquid separation container 9 is disposed above the desulfurizer 8, and the liquid fuel and the gas flow line 12 for supplying the liquid fuel and the gas are connected to one end of the desulfurizer 8 and the other end to the gas-liquid separation container 9 The bottom walls are connected. Thereby, the gas discharged from the desulfurizer 8 can be surely introduced into the gas-liquid separation container 9. Further, although not shown, in order to remove the desulfurization catalyst contained in the liquid fuel from which the sulfur component has been removed by the desulfurizer 8, a filter is provided in the liquid fuel and gas flow line 12. In the present embodiment, for example, a filter having a mesh of about 0.026 mm can be used.

氣液分離容器9之頂壁與氣體排出管線13之一端相連接，該氣體排出管線13用於將儲存在氣液分離容器9內之上方之氣體自氣液分離容器9排出。氣體排出管線13之另一端與對改質器5之改質觸媒進行加熱之燃燒器6相連接。在氣體排出管線13上設有開啟及關閉氣體之流通之電磁閥14。電磁閥14與氣液分離容器9協同動作，構成自液體燃料中除去氣體之除氣器D。並且，在氣體排出管線13上之電磁閥14之下游側設有阻礙氣體流通之毛細管15。又，氣體排出管線13上之毛細管15之下游側與設有用於將空氣導入至燃燒器6中之泵16之空氣流通管線17相連接。 The top wall of the gas-liquid separation container 9 is connected to one end of a gas discharge line 13 for discharging the gas stored above the gas-liquid separation container 9 from the gas-liquid separation container 9. The other end of the gas discharge line 13 is connected to a burner 6 that heats the reforming catalyst of the reformer 5. A solenoid valve 14 that opens and closes the flow of the gas is provided in the gas discharge line 13. The solenoid valve 14 cooperates with the gas-liquid separation container 9 to constitute a deaerator D that removes gas from the liquid fuel. Further, a capillary 15 that blocks the flow of the gas is provided on the downstream side of the electromagnetic valve 14 on the gas discharge line 13. Further, the downstream side of the capillary 15 on the gas discharge line 13 is connected to an air circulation line 17 provided with a pump 16 for introducing air into the burner 6.

另一方面，氣液分離容器9之底壁與液體燃料排出管線18之一端相連接，該液體燃料排出管線18用於將儲存在氣液分離容器9內之下方之液體燃料自氣液分離容器9排出。液體燃料排出管線18之另一端與配置在氣液分離容器9上方之儲存容器19之側壁相連接。在液體燃 料排出管線18上設有阻礙液體燃料流通之毛細管21。 On the other hand, the bottom wall of the gas-liquid separation container 9 is connected to one end of a liquid fuel discharge line 18 for separating the liquid fuel stored in the gas-liquid separation container 9 from the gas-liquid separation container. 9 discharge. The other end of the liquid fuel discharge line 18 is connected to the side wall of the storage container 19 disposed above the gas-liquid separation container 9. In liquid burning The material discharge line 18 is provided with a capillary 21 that blocks the flow of the liquid fuel.

此處，毛細管21係將極細管捲繞成螺旋狀而成者。毛細管21之內徑及被捲繞時之直徑係設定為在由恆壓泵決定之壓力下，液體燃料之流量為低流量(例如，在1kW之燃料電池系統時為10g/min以下)。具體而言，較好的是毛細管21之內徑為0.1mm~0.7mm左右，較好的是被捲繞成螺旋之直徑為10mm~100mm左右。毛細管21之全長在第6實施形態中為600mm左右，但可考慮所需之流量、所需之脫硫器8內之壓力、毛細管21之內徑及捲繞毛細管21時之直徑而設定。如上所述，雖在液體燃料、氣體流通管線12上設有過濾器，但粒徑比網眼小之脫硫觸媒會通過過濾器，因此，當毛細管21之內徑未達0.1mm時，存在脫硫觸媒容易堵塞毛細管21之傾向。另一方面，當毛細管21之內徑超過0.7mm時，為將脫硫器8內維持為高壓並且以低流量進行液體燃料之輸送，導致所需之毛細管21之全長變長，從而存在難以小型化之傾向。再者，可根據毛細管21被捲繞時之直徑之大小而調整壓損。 Here, the capillary 21 is obtained by winding a very thin tube into a spiral shape. The inner diameter of the capillary 21 and the diameter at the time of winding are set such that the flow rate of the liquid fuel is a low flow rate under a pressure determined by the constant pressure pump (for example, 10 g/min or less in a fuel cell system of 1 kW). Specifically, it is preferable that the inner diameter of the capillary 21 is about 0.1 mm to 0.7 mm, and it is preferable that the diameter of the spiral is about 10 mm to 100 mm. The total length of the capillary 21 is about 600 mm in the sixth embodiment, but it can be set in consideration of the required flow rate, the pressure in the required desulfurizer 8, the inner diameter of the capillary 21, and the diameter when the capillary 21 is wound. As described above, although the filter is provided on the liquid fuel and gas circulation line 12, the desulfurization catalyst having a smaller particle diameter than the mesh passes through the filter, and therefore, when the inner diameter of the capillary 21 is less than 0.1 mm, There is a tendency that the desulfurization catalyst easily blocks the capillary 21. On the other hand, when the inner diameter of the capillary 21 exceeds 0.7 mm, in order to maintain the high pressure inside the desulfurizer 8 and carry out the transportation of the liquid fuel at a low flow rate, the total length of the required capillary 21 becomes long, so that it is difficult to be small. The tendency to change. Further, the pressure loss can be adjusted according to the diameter of the capillary 21 when it is wound.

儲存容器19之底壁與液體燃料流通管線23、液體燃料流通管線25相連接，該液體燃料流通管線23上設有用於將儲存在儲存容器19內之下方之液體燃料導入至改質器5中之泵22，該液體燃料流通管線25上設有用於將該液體燃料導入至燃燒器6中之泵24。如此，藉由將液體燃料暫時儲存在儲存容器19中，可使泵22對改質器5之液體燃料之供給及泵24對燃燒器6之液體燃料之供給穩定化。 The bottom wall of the storage container 19 is connected to the liquid fuel circulation line 23 and the liquid fuel circulation line 25, and the liquid fuel circulation line 23 is provided with a liquid fuel for being stored in the storage container 19 to be introduced into the reformer 5. The pump 22 is provided with a pump 24 for introducing the liquid fuel into the burner 6. Thus, by temporarily storing the liquid fuel in the storage container 19, the supply of the liquid fuel to the reformer 5 by the pump 22 and the supply of the liquid fuel to the burner 6 by the pump 24 can be stabilized.

在如上所述般構成之燃料電池系統1中，液體燃料首先被導入至脫硫器8中，在脫硫器8中，在高溫、高壓之狀態下利用脫硫觸媒自液體燃料中除去硫成分。自脫硫器8排出之液體燃料及氣體被儲存至氣液分離器9中，液體燃料經由液體燃料排出管線18、儲存容器19及液體流通管線23而導入至改質室5中。此時，液體燃料經由液體燃料排出管線18、儲存容器19及液體流通管線25而導入至燃燒器6中，並且 空氣經由空氣流通管線17被導入至燃燒器6中。藉此，在改質器5中，改質觸媒被進行燃燒之燃燒器6加熱，使用液體燃料而生成改質氣體。在改質器5中生成之改質氣體被導入至燃料電池堆疊4中，在燃料電池堆疊4中，使用改質氣體進行發電。 In the fuel cell system 1 configured as described above, the liquid fuel is first introduced into the desulfurizer 8, and in the desulfurizer 8, the sulfur is removed from the liquid fuel by the desulfurization catalyst at a high temperature and a high pressure. ingredient. The liquid fuel and gas discharged from the desulfurizer 8 are stored in the gas-liquid separator 9, and the liquid fuel is introduced into the reforming chamber 5 via the liquid fuel discharge line 18, the storage container 19, and the liquid flow line 23. At this time, the liquid fuel is introduced into the combustor 6 via the liquid fuel discharge line 18, the storage container 19, and the liquid circulation line 25, and Air is introduced into the combustor 6 via the air circulation line 17. Thereby, in the reformer 5, the reforming catalyst is heated by the burner 6 that performs combustion, and the reformed gas is generated using the liquid fuel. The reformed gas generated in the reformer 5 is introduced into the fuel cell stack 4, and in the fuel cell stack 4, the reformed gas is used for power generation.

另一方面，被儲存在氣液分離容器9中之氣體經由氣體排出管線13而導入至燃燒器6中，與液體燃料一起用作燃燒器6之燃料。如此，可有效地利用與液體燃料一起自脫硫器8排出之氣體作為燃燒器6之燃料。再者，電磁閥14在關閉氣體之流通之情形時，在由浮動開關11檢測之氣液分離容器9內之氣體之量超過特定量時，電磁閥14分多次開啟氣體之流通。 On the other hand, the gas stored in the gas-liquid separation container 9 is introduced into the burner 6 via the gas discharge line 13, and serves as a fuel for the burner 6 together with the liquid fuel. Thus, the gas discharged from the desulfurizer 8 together with the liquid fuel can be effectively utilized as the fuel of the burner 6. Further, when the solenoid valve 14 closes the flow of the gas, when the amount of the gas in the gas-liquid separation container 9 detected by the float switch 11 exceeds a certain amount, the solenoid valve 14 opens the gas flow a plurality of times.

在如上所述之第6實施形態中，將毛細管21配置在脫硫器8之下游側。因此，藉由適當地選擇毛細管21之內徑及長度，不使用高價之泵，便可使脫硫器8內之壓力及液體燃料之流量達到期望之大小。其結果，可簡便且低成本地實現以低流量輸送液體燃料。 In the sixth embodiment as described above, the capillary 21 is disposed on the downstream side of the desulfurizer 8. Therefore, by appropriately selecting the inner diameter and length of the capillary 21, the pressure in the desulfurizer 8 and the flow rate of the liquid fuel can be made to a desired size without using a high-priced pump. As a result, the liquid fuel can be delivered at a low flow rate simply and at low cost.

一般認為亦可利用節流孔、針型閥等替代毛細管21。然而，延長節流孔部分之流路存在極限，因此為減小自脫硫器8被排出之高壓之液體燃料之流量而必需使節流孔部分之直徑很小。此處，在脫硫器8中藉由脫硫觸媒進行液體燃料之脫硫，但有時脫硫觸媒會包含於藉由脫硫器8除去了硫成分之液體燃料中。因此，在利用節流孔、針型閥等之情形時，自脫硫器8流出之脫硫觸媒有時會堵塞節流孔部分之流路。 It is generally considered that an orifice 21, a needle valve, or the like can be used instead of the capillary 21. However, there is a limit to the flow path for extending the orifice portion, so that the diameter of the orifice portion must be made small in order to reduce the flow rate of the high-pressure liquid fuel discharged from the desulfurizer 8. Here, the desulfurizer 8 performs desulfurization of the liquid fuel by a desulfurization catalyst, but sometimes the desulfurization catalyst is contained in the liquid fuel from which the sulfur component is removed by the desulfurizer 8. Therefore, in the case of using an orifice, a needle valve, or the like, the desulfurization catalyst flowing out of the desulfurizer 8 sometimes blocks the flow path of the orifice portion.

然而，在第6實施形態之燃料電池系統1中，如上所述般使用毛細管21，因此，根據毛細管21之長度，可在一定程度上增大毛細管21之內徑。因此，極難發生由脫硫觸媒引起之堵塞之情況。 However, in the fuel cell system 1 of the sixth embodiment, since the capillary 21 is used as described above, the inner diameter of the capillary 21 can be increased to some extent depending on the length of the capillary 21. Therefore, it is extremely difficult to cause clogging caused by the desulfurization catalyst.

以上對本發明之第6側面之較佳實施形態進行了詳細說明，但本發明之第6側面不限於上述實施形態。例如，燃料電池堆疊4不限於固 體高分子型燃料電池堆疊，亦可為固體氧化物型燃料電池堆疊等。 Although the preferred embodiment of the sixth aspect of the present invention has been described in detail above, the sixth aspect of the present invention is not limited to the above embodiment. For example, the fuel cell stack 4 is not limited to solid The bulk polymer fuel cell stack may also be a solid oxide fuel cell stack or the like.

又，改質器5不限於水蒸氣改質之改質器，亦可為部分氧化改質、自身熱改質之改質器。改質器5之改質方法除根據煤油之特性而設以外，還根據汽油、石腦油、輕油、甲醇、乙醇、DME(二甲醚)、利用生物物質之生物燃料等液體燃料之特性而設。 Moreover, the reformer 5 is not limited to a reformer that is modified by steam, and may be a reformer that is partially oxidized and modified by itself. The reforming method of the reformer 5 is based on the characteristics of kerosene, and is based on the characteristics of liquid fuels such as gasoline, naphtha, light oil, methanol, ethanol, DME (dimethyl ether), biofuels using biomass, and the like. And set.

又，亦可使用定流量泵替代恆壓泵7。但自脫硫器8內之壓力管理之觀點考慮，較好的是使用恆壓泵7。 Alternatively, a constant flow pump can be used instead of the constant pressure pump 7. However, it is preferable to use the constant pressure pump 7 from the viewpoint of pressure management in the desulfurizer 8.

又，如圖23所示，亦可不在燃料電池系統1中設置除氣器D、氣體排出管線13及毛細管15。即，亦可利用液體燃料、氣體流通管線12將脫硫器8及儲存容器19直接連接，並在液體燃料、氣體流通管線12上設置毛細管21。再者，此時，泵16及燃燒器6藉由空氣流通管線17而直接連接。 Further, as shown in FIG. 23, the deaerator D, the gas discharge line 13, and the capillary 15 may not be provided in the fuel cell system 1. In other words, the desulfurizer 8 and the storage container 19 can be directly connected by the liquid fuel and the gas flow line 12, and the capillary 21 can be provided in the liquid fuel and the gas flow line 12. Further, at this time, the pump 16 and the burner 6 are directly connected by the air circulation line 17.

3‧‧‧脫硫裝置 3‧‧‧Desulfurization unit

7‧‧‧脫硫觸媒 7‧‧‧Desulfurization catalyst

7a‧‧‧脫硫器 7a‧‧‧Desulfurizer

8‧‧‧加熱器(加熱機構) 8‧‧‧heater (heating mechanism)

9‧‧‧入口閥(液體燃料導入機構) 9‧‧‧Inlet valve (liquid fuel introduction mechanism)

11‧‧‧泵(液體燃料導入機構) 11‧‧‧ pump (liquid fuel introduction mechanism)

12‧‧‧出口閥(液體燃料導出機構) 12‧‧‧Export valve (liquid fuel export mechanism)

13‧‧‧溫度計(溫度測量機構) 13‧‧‧ Thermometer (temperature measuring mechanism)

14‧‧‧壓力計(壓力測量機構) 14‧‧‧ Pressure gauge (pressure measuring mechanism)

15‧‧‧控制部(控制機構) 15‧‧‧Control Department (Control Agency)

Claims (8)

一種燃料電池系統，其特徵在於包括：泵，其送出液體燃料；脫硫器，其配置在上述泵之下游側，並將硫成分自上述液體燃料中除去；毛細管，其配置在上述脫硫器之下游側，供經上述脫硫器除去硫成分後之液體燃料通過；改質器，其配置在上述毛細管之下游側，使用經上述脫硫器除去硫成分後之液體燃料生成含有氫之改質氣體；以及燃料電池堆疊，其使用由上述改質器所生成之上述改質氣體進行發電。 A fuel cell system, comprising: a pump that delivers liquid fuel; a desulfurizer disposed on a downstream side of the pump and removing sulfur components from the liquid fuel; and a capillary tube disposed in the desulfurizer On the downstream side, the liquid fuel after removing the sulfur component by the desulfurizer passes; the reformer is disposed on the downstream side of the capillary, and the liquid fuel containing the sulfur component is removed by the desulfurizer to generate hydrogen. And a fuel cell stack that uses the above-described reformed gas generated by the reformer to generate electricity. 如請求項1之燃料電池系統，其中上述泵係恆壓泵。 The fuel cell system of claim 1, wherein the pump is a constant pressure pump. 如請求項1之燃料電池系統，其中上述毛細管之內徑為0.1mm~0.7mm。 The fuel cell system of claim 1, wherein the capillary has an inner diameter of 0.1 mm to 0.7 mm. 如請求項1之燃料電池系統，其中上述毛細管係捲繞成螺旋狀。 The fuel cell system of claim 1, wherein the capillary system is wound in a spiral shape. 一種改質系統，其特徵在於包括：泵，其送出液體燃料；脫硫器，其配置在上述泵之下游側，並將硫成分自上述液體燃料中除去；毛細管，其配置在上述脫硫器之下游側，供經上述脫硫器除去硫成分後之液體燃料通過；以及改質器，其配置在上述毛細管之下游側，使用經上述脫硫器除 去硫成分後之液體燃料生成含有氫之改質氣體。 A upgrading system, comprising: a pump for sending liquid fuel; a desulfurizer disposed on a downstream side of the pump and removing sulfur components from the liquid fuel; and a capillary tube disposed in the desulfurizer a downstream side of the liquid fuel through which the sulfur component is removed by the desulfurizer; and a reformer disposed on the downstream side of the capillary tube and removed by the desulfurizer The liquid fuel after desulfurization produces a reformed gas containing hydrogen. 如請求項5之改質系統，其中上述泵係恆壓泵。 The upgrading system of claim 5, wherein the pump is a constant pressure pump. 如請求項5之改質系統，其中上述毛細管之內徑為0.1mm~0.7mm。 The modified system of claim 5, wherein the inner diameter of the capillary is 0.1 mm to 0.7 mm. 如請求項5之改質系統，其中上述毛細管係捲繞成螺旋狀。 The modified system of claim 5, wherein the capillary system is wound into a spiral shape.
TW103114082A 2008-05-14 2009-04-14 Desulfurizing device and fuel cell system TW201429037A (en)

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JP2008127362A JP5171384B2 (en) 2008-05-14 2008-05-14 Desulfurization apparatus and fuel cell system
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JP2008159467A JP4918068B2 (en) 2008-06-18 2008-06-18 Fuel cell system
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
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