JP2009107888A - Apparatus for producing reforming raw material and fuel cell system - Google Patents

Apparatus for producing reforming raw material and fuel cell system Download PDF

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JP2009107888A
JP2009107888A JP2007282107A JP2007282107A JP2009107888A JP 2009107888 A JP2009107888 A JP 2009107888A JP 2007282107 A JP2007282107 A JP 2007282107A JP 2007282107 A JP2007282107 A JP 2007282107A JP 2009107888 A JP2009107888 A JP 2009107888A
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water
vaporizer
desulfurizer
raw material
liquid fuel
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JP5129544B2 (en
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Susumu Hatada
進 旗田
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Eneos Corp
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Nippon Oil Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • C01B2203/1294—Evaporation by heat exchange with hot process stream
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Electrochemistry (AREA)
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  • Organic Chemistry (AREA)
  • Fuel Cell (AREA)
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  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus for producing a reforming raw material, wherein a desulfurizing agent in a desulfurizer can be easily and surely maintained at a proper temperature. <P>SOLUTION: In the apparatus 4 for producing the reforming raw material for the fuel cell system 1, a desulfurizer 6 for removing a sulfur component from a liquid fuel is disposed so as to be immersed in the water L in the liquid phase state within a water vaporizer 5, which heats water L in a liquid phase state, through heat exchange with an off gas discharged from an solid oxide fuel cell (SOFC) stack 3, to vaporize the water L. According to this constitution, the desulfurizing agent in the desulfurizer 6 is heated to a temperature close to the boiling point of the water L in the liquid phase state by heat exchange with the water L in the liquid phase state, stored in the water vaporizer 5. In this case, the pressure of water V in a gas phase state within the water vaporizer 5 is controlled through an orifice 7 provided in a water vapor supply line 18. Accordingly, the boiling point of the water within the water vaporizer is controlled to a predetermined temperature. Thus, the desulfurizing agent in the desulfurizer 6 can be easily and surely maintained at the proper temperature. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、水素を含有する改質ガスを生成する改質器に供給される改質原料を製造する改質原料製造装置、及びそのような改質原料製造装置を備える燃料電池システムに関する。   The present invention relates to a reformed raw material production apparatus that produces a reformed raw material that is supplied to a reformer that generates a reformed gas containing hydrogen, and a fuel cell system including such a reformed raw material production apparatus.

燃料電池システムは、例えば、灯油等の液体燃料を改質して水素を含有する改質ガスを生成する改質器と、改質ガス及び空気を電気化学的に発電反応させるセルスタックと、を備えている。改質器に供給される液体燃料からは、改質器内の改質触媒が被毒されるのを防止するために、脱硫器内の脱硫剤によって硫黄分（硫黄や硫黄化合物等）が除去される。そして、脱硫器の加熱は、改質器を加熱するバーナから排出される燃焼ガスよって行われる場合がある（例えば、特許文献１，２参照）。
特開平５−３０４３号公報 特開２００２−２０１４７８号公報 The fuel cell system includes, for example, a reformer that reforms liquid fuel such as kerosene to generate a reformed gas containing hydrogen, and a cell stack that electrochemically generates and reacts the reformed gas and air. I have. In order to prevent the reforming catalyst in the reformer from being poisoned, sulfur (sulfur, sulfur compounds, etc.) is removed from the liquid fuel supplied to the reformer by the desulfurization agent in the desulfurizer. Is done. The desulfurizer may be heated by combustion gas discharged from a burner that heats the reformer (see, for example, Patent Documents 1 and 2).
Japanese Patent Laid-Open No. 5-3043 JP 2002-2014478 A

しかしながら、改質器を加熱するバーナから排出される燃焼ガスよって脱硫器の加熱が行われる場合、燃焼ガスの熱量が変化して、脱硫器内の脱硫剤が適正な温度に維持されず、液体燃料から硫黄分が十分に除去されないおそれがある。   However, when the desulfurizer is heated by the combustion gas discharged from the burner that heats the reformer, the amount of heat of the combustion gas changes and the desulfurizing agent in the desulfurizer is not maintained at an appropriate temperature, and the liquid Sulfur content may not be sufficiently removed from the fuel.

そこで、本発明は、このような事情に鑑みてなされたものであり、脱硫器内の脱硫剤を適正な温度に容易且つ確実に維持することができる改質原料製造装置、及びそのような改質原料製造装置を備える燃料電池システムを提供することを目的とする。   Therefore, the present invention has been made in view of such circumstances, and a reforming raw material manufacturing apparatus capable of easily and reliably maintaining a desulfurizing agent in a desulfurizer at an appropriate temperature, and such a modification. It aims at providing a fuel cell system provided with a quality raw material manufacturing apparatus.

上記目的を達成するために、本発明に係る改質原料製造装置は、水素を含有する改質ガスを生成する改質器に供給される改質原料を製造する改質原料製造装置であって、改質原料となる水を気化させる水気化器と、水気化器内に配置され、改質原料となる液体燃料から硫黄分を除去する脱硫器と、水気化器内の圧力を調整する圧力調整器と、を備えることを特徴とする。   In order to achieve the above object, a reformed raw material production apparatus according to the present invention is a reformed raw material production apparatus for producing a reformed raw material to be supplied to a reformer that generates a reformed gas containing hydrogen. , A water vaporizer that vaporizes water as the reforming raw material, a desulfurizer that is disposed in the water vaporizer and removes sulfur from the liquid fuel that is the reforming raw material, and a pressure that adjusts the pressure in the water vaporizer And a regulator.

この改質原料製造装置では、改質原料となる水を気化させる水気化器内に、改質原料となる液体燃料から硫黄分を除去する脱硫器が配置されているため、水の沸点近傍の温度に脱硫器内の脱硫剤が加熱される。このとき、圧力調整器によって水気化器内の圧力が調整されるため、水気化器内の水の沸点が所定の温度に調整される。以上により、脱硫器内の脱硫剤を適正な温度に容易且つ確実に維持することが可能となる。   In this reformed raw material manufacturing apparatus, a desulfurizer that removes sulfur from the liquid fuel that is the reforming raw material is disposed in the water vaporizer that vaporizes the water that is the reforming raw material. The desulfurization agent in the desulfurizer is heated to the temperature. At this time, since the pressure in the water vaporizer is adjusted by the pressure regulator, the boiling point of the water in the water vaporizer is adjusted to a predetermined temperature. As described above, the desulfurizing agent in the desulfurizer can be easily and reliably maintained at an appropriate temperature.

本発明に係る改質原料製造装置においては、水気化器内には、脱硫器によって硫黄分が除去された液体燃料を気化させる液体燃料気化器が配置されており、水気化器によって気化させられた水と液体燃料気化器によって気化させられた液体燃料とは、水気化器内おいて混合されて改質原料とされることが好ましい。この場合、脱硫器だけでなく液体燃料気化器も水気化器内に配置されるため、改質原料製造装置の小型化を図ることができる。   In the reforming raw material production apparatus according to the present invention, a liquid fuel vaporizer that vaporizes liquid fuel from which sulfur content has been removed by a desulfurizer is disposed in the water vaporizer, and is vaporized by the water vaporizer. It is preferable that the water and the liquid fuel vaporized by the liquid fuel vaporizer are mixed in the water vaporizer and used as a reforming raw material. In this case, since not only the desulfurizer but also the liquid fuel vaporizer is arranged in the water vaporizer, it is possible to reduce the size of the reforming raw material production apparatus.

本発明に係る燃料電池システムは、上記改質原料製造装置と、改質原料製造装置によって製造された改質原料を用いて改質ガスを生成する改質器と、改質器によって生成された改質ガスを用いて発電を行う燃料電池スタックと、を備えることを特徴とする。   A fuel cell system according to the present invention is produced by the above reformed raw material production apparatus, a reformer that produces a reformed gas using the reformed raw material produced by the reformed raw material production apparatus, and the reformer. And a fuel cell stack that generates power using the reformed gas.

この燃料電池システムによれば、上記改質原料製造装置が設けられているため、脱硫器内の脱硫剤を適正な温度に容易且つ確実に維持することが可能となる。   According to this fuel cell system, since the reforming raw material production apparatus is provided, the desulfurization agent in the desulfurizer can be easily and reliably maintained at an appropriate temperature.

本発明によれば、脱硫器内の脱硫剤を適正な温度に容易且つ確実に維持することができる。   According to the present invention, the desulfurizing agent in the desulfurizer can be easily and reliably maintained at an appropriate temperature.

以下、本発明の好適な実施形態について、図面を参照して詳細に説明する。なお、各図において同一又は相当部分には同一符号を付し、重複する説明を省略する。
［第１の実施形態］ DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In addition, in each figure, the same code | symbol is attached | subjected to the same or an equivalent part, and the overlapping description is abbreviate | omitted.
[First Embodiment]

図１は、本発明に係る燃料電池システムの第１の実施形態の構成図である。図１に示されるように、燃料電池システム１は、原燃料を水蒸気改質して水素を含有する改質ガスを生成する改質器２と、改質器２によって生成された改質ガス及び空気を電気化学的に発電反応させる固体酸化物形燃料電池（Solid Oxide Fuel Cell：ＳＯＦＣ）スタック（燃料電池スタック）３と、改質器２に供給するために改質原料を製造する改質原料製造装置４と、を備えている。   FIG. 1 is a configuration diagram of a first embodiment of a fuel cell system according to the present invention. As shown in FIG. 1, a fuel cell system 1 includes a reformer 2 that generates a reformed gas containing hydrogen by steam reforming a raw fuel, a reformed gas generated by the reformer 2, and A solid oxide fuel cell (SOFC) stack (fuel cell stack) 3 that generates electricity electrochemically and reacts with air, and a reforming material that produces reforming material to be supplied to the reformer 2 And a manufacturing apparatus 4.

改質原料製造装置４は、改質原料となる水を気化させる水気化器５と、改質原料となる液体燃料から硫黄分を除去する脱硫器６と、水気化器５内の圧力を調整するオリフィス（圧力調整器）７と、脱硫器６によって硫黄分が除去された液体燃料を気化させる液体燃料気化器８と、を備えている。   The reforming raw material manufacturing apparatus 4 adjusts the pressure in the water vaporizer 5, the water vaporizer 5 that vaporizes the water that is the reforming raw material, the desulfurizer 6 that removes sulfur from the liquid fuel that is the reforming raw material, and the water vaporizer 5. An orifice (pressure regulator) 7 and a liquid fuel vaporizer 8 for vaporizing the liquid fuel from which the sulfur content has been removed by the desulfurizer 6.

液体燃料としては、ガソリン、ナフサ、灯油等の石油系燃料、メタノール等のアルコール等、常温、常圧（２５℃、０．１ＭＰａ）で液体である炭化水素系の燃料、或いは液化石油ガスを用いることができる。なかでも灯油は工業用としても民生用としても入手容易であり、その取り扱いも容易なため、好ましい。   As the liquid fuel, petroleum-based fuels such as gasoline, naphtha and kerosene, alcohols such as methanol, etc., hydrocarbon-based fuels that are liquid at normal temperature and normal pressure (25 ° C., 0.1 MPa), or liquefied petroleum gas are used. be able to. Of these, kerosene is preferable because it is easily available for industrial use and consumer use, and is easy to handle.

脱硫後の液体燃料中の硫黄濃度は、改質装置に液体燃料を供給する場合に改質触媒の被毒を抑制する観点から、好ましくは０．１質量ｐｐｍ以下、より好ましくは５０質量ｐｐｂ以下とする。   The sulfur concentration in the liquid fuel after desulfurization is preferably 0.1 mass ppm or less, more preferably 50 mass ppb or less, from the viewpoint of suppressing poisoning of the reforming catalyst when the liquid fuel is supplied to the reformer. And

脱硫に供する液体燃料中の硫黄濃度には特に制限はなく、脱硫工程において上記硫黄濃度に転換できる液体燃料であれば使用することができる。ただし、脱硫剤の寿命の観点からは、液体燃料の硫黄濃度は、１５０質量ｐｐｍ以下が好ましく、５０質量ｐｐｍ以下がより好ましい。   There is no restriction | limiting in particular in the sulfur concentration in the liquid fuel with which it uses for desulfurization, If it is a liquid fuel which can be converted into the said sulfur concentration in a desulfurization process, it can be used. However, from the viewpoint of the life of the desulfurizing agent, the sulfur concentration of the liquid fuel is preferably 150 ppm by mass or less, and more preferably 50 ppm by mass or less.

ＳＯＦＣスタック３は、改質ガス導入ライン１１を介して改質器２と接続され、空気導入ライン１２を介して空気ブロア（図示せず）と接続されている。空気導入ライン１２には、空気の導入量を調整する電磁バルブ（図示せず）や空気予熱器（図示せず）が設けられている。ＳＯＦＣスタック３や空気予熱器は、筐体１３内に収容されている。   The SOFC stack 3 is connected to the reformer 2 via a reformed gas introduction line 11 and is connected to an air blower (not shown) via an air introduction line 12. The air introduction line 12 is provided with an electromagnetic valve (not shown) and an air preheater (not shown) for adjusting the amount of air introduced. The SOFC stack 3 and the air preheater are accommodated in the housing 13.

ＳＯＦＣスタック３は、複数の単セルスタック３ａが積層されて構成されている。単セルスタック３ａは、アノード（燃料極）と、カソード（空気極）と、アノードとカソードとの間に配置された電解質と、アノード及びカソードの外側にそれぞれ配置されたセパレータと、を有している。アノードには、改質器２から改質ガス導入ライン１１を介して改質ガスが導入され、カソードには、空気ブロアから空気導入ライン１２を介して空気が導入される。これにより、各単セルスタック３ａにおいて電気化学的な発電反応が行われることになる。   The SOFC stack 3 is configured by stacking a plurality of single cell stacks 3a. The single cell stack 3a includes an anode (fuel electrode), a cathode (air electrode), an electrolyte disposed between the anode and the cathode, and a separator disposed respectively outside the anode and the cathode. Yes. The reformed gas is introduced from the reformer 2 through the reformed gas introduction line 11 to the anode, and air is introduced from the air blower through the air introduction line 12 to the cathode. Thereby, electrochemical power generation reaction is performed in each single cell stack 3a.

水気化器５は、ステンレス鋼等の金属からなる円筒状の容器であり、ＳＯＦＣスタック３からオフガスを排出するためのオフガス排出流路１４内に配置されている。水気化器５内の下側部分に貯留された液相状態の水Ｌは、オフガス排出流路１４内を流通するオフガスとの熱交換で加熱され、気化して気相状態の水Ｖとなる。気相状態の水Ｖは、水気化器５内の上側部分に充満する。   The water vaporizer 5 is a cylindrical container made of a metal such as stainless steel, and is disposed in an offgas discharge channel 14 for discharging offgas from the SOFC stack 3. The liquid-phase water L stored in the lower part of the water vaporizer 5 is heated by heat exchange with off-gas flowing through the off-gas discharge passage 14 and vaporized to become vapor-phase water V. . The vapor phase water V fills the upper part of the water vaporizer 5.

水気化器５の底壁５ａには、水（液相状態の水Ｌ）を水気化器５内に導入するための水導入部１５が設けられている。水導入部１５は、水供給ライン１６を介して水タンク（図示せず）と接続されており、水供給ライン１６には、水タンクから水気化器５に水を圧送するためのポンプ（図示せず）が設けられている。また、水気化器５の側壁５ｂの上部には、水蒸気（気相状態の水Ｖ）を水気化器５外に導出するための水蒸気導出部１７が設けられている。水蒸気導出部１７は、水蒸気供給ライン１８及び改質原料供給ライン２５を介して改質器２と接続されている。水気化器５内の圧力を調整するオリフィス７は、水蒸気供給ライン１８に設けられている。   On the bottom wall 5 a of the water vaporizer 5, a water introduction unit 15 for introducing water (liquid phase water L) into the water vaporizer 5 is provided. The water introduction part 15 is connected to a water tank (not shown) via a water supply line 16, and a pump (not shown) for pumping water from the water tank to the water vaporizer 5 is connected to the water supply line 16. Not shown). Further, a water vapor deriving unit 17 for deriving water vapor (vapor phase water V) to the outside of the water vaporizer 5 is provided on the upper portion of the side wall 5 b of the water vaporizer 5. The steam outlet 17 is connected to the reformer 2 via a steam supply line 18 and a reforming raw material supply line 25. The orifice 7 for adjusting the pressure in the water vaporizer 5 is provided in the water vapor supply line 18.

脱硫器６は、その内部に脱硫剤が設けられたものであり、液相状態の水Ｌに浸漬されるように水気化器５内に配置され、水気化器５の底壁５ａに固定されている。脱硫器６内に導入された液体燃料は、水気化器５内に貯留された液相状態の水Ｌとの熱交換で水の沸点近傍の温度に加熱された脱硫剤によって硫黄分を除去され、脱硫器６外に導出される。   The desulfurizer 6 is provided with a desulfurizing agent therein, and is disposed in the water vaporizer 5 so as to be immersed in the water L in the liquid phase, and is fixed to the bottom wall 5 a of the water vaporizer 5. ing. The liquid fuel introduced into the desulfurizer 6 is desulfurized by a desulfurization agent heated to a temperature near the boiling point of water by heat exchange with the liquid phase water L stored in the water vaporizer 5. , And is led out of the desulfurizer 6.

脱硫剤としては、収着型脱硫剤など公知の脱硫剤を用いればよいが、例えば、Ｎｉ、Ｃｕ、Ｚｎ及びＦｅから選ばれる少なくとも１種類の金属を含み、担体にシリカ、アルミナ、チタニア、ジルコニア、マグネシア及びその複合酸化物から選ばれる少なくとも一種を用いたもの、又はこれらの成分を共沈で生成したものを使用することができる。なかでも少なくともＮｉを含有する収着剤が触媒寿命の観点から好ましい。   As the desulfurizing agent, a known desulfurizing agent such as a sorption desulfurizing agent may be used. For example, the desulfurizing agent contains at least one metal selected from Ni, Cu, Zn, and Fe, and the carrier is silica, alumina, titania, zirconia. In addition, those using at least one selected from magnesia and complex oxides thereof, or those produced by coprecipitation of these components can be used. Among them, a sorbent containing at least Ni is preferable from the viewpoint of catalyst life.

脱硫剤形状としては、特に限りはないが、円柱、三つ葉、四葉などの押し出し成型体、円柱、ドーム状の錠剤成型体、球状成型体が好ましい。   The shape of the desulfurizing agent is not particularly limited, but an extruded molded body such as a cylinder, a trefoil, and a four leaf, a cylinder, a dome-shaped tablet molded body, and a spherical molded body are preferable.

脱硫器６の底壁には、液体燃料を脱硫器６内に導入するための液体燃料導入部２１が設けられている。液体燃料導入部２１は、液体燃料供給ライン２２を介して液体燃料タンク（図示せず）と接続されており、液体燃料供給ライン２２には、液体燃料タンクから脱硫器６に液体燃料を圧送するためのポンプ（図示せず）が設けられている。また、脱硫器６の天井壁には、硫黄分が除去された液体燃料を脱硫器６外に導出するためのパイプ状の液体燃料導出部２３が設けられている。液体燃料導出部２３は、水気化器５の天井壁５ｃを気密に貫通しており、液体燃料供給ライン２４及び改質原料供給ライン２５を介して改質器２と接続されている。脱硫器６によって硫黄分が除去された液体燃料を気化させる液体燃料気化器８は、液体燃料供給ライン２４に設けられている。   A liquid fuel introduction part 21 for introducing liquid fuel into the desulfurizer 6 is provided on the bottom wall of the desulfurizer 6. The liquid fuel introduction unit 21 is connected to a liquid fuel tank (not shown) via a liquid fuel supply line 22, and the liquid fuel is pumped from the liquid fuel tank to the desulfurizer 6 through the liquid fuel supply line 22. A pump (not shown) is provided. In addition, a pipe-shaped liquid fuel lead-out portion 23 is provided on the ceiling wall of the desulfurizer 6 to lead out the liquid fuel from which sulfur has been removed to the outside of the desulfurizer 6. The liquid fuel outlet 23 penetrates the ceiling wall 5 c of the water vaporizer 5 in an airtight manner, and is connected to the reformer 2 via the liquid fuel supply line 24 and the reforming raw material supply line 25. The liquid fuel vaporizer 8 that vaporizes the liquid fuel from which the sulfur content has been removed by the desulfurizer 6 is provided in the liquid fuel supply line 24.

脱硫剤に対する液体燃料の供給量は、装置サイズ、経済性および脱硫速度の観点から、ＬＨＳＶ（液空間速度）で０．０５ｈｒ-1以上５．０ｈｒ-1以下が好ましく、０．１ｈｒ-1以上３．０ｈｒ-1以下がより好ましく、０．５ｈｒ-1前後が特に好ましい。 The supply amount of the liquid fuel to the desulfurizing agent, the device size, in terms of economy and desulfurization rate, preferably 0.05Hr -1 or more 5.0Hr -1 or less at LHSV (liquid hourly space velocity), 0.1 hr -1 or more 3.0 hr −1 or less is more preferable, and around 0.5 hr −1 is particularly preferable.

改質原料製造装置４は、水蒸気供給ライン１８と液体燃料供給ライン２４とが合流する改質原料供給ライン２５を介して改質器２に改質原料を供給する。改質原料は、水気化器５によって気化させられた水蒸気（液相状態の水Ｌが気化させられたもの：気相状態の水Ｖ）と、脱硫器６によって硫黄分が除去され且つ液体燃料気化器８によって気化させられた燃料ガス（液体燃料が気化させられたもの）との混合ガスである。   The reforming material manufacturing apparatus 4 supplies the reforming material to the reformer 2 via the reforming material supply line 25 where the steam supply line 18 and the liquid fuel supply line 24 merge. The reforming raw material is vaporized by the water vaporizer 5 (water in which the liquid phase water L is vaporized: water V in the gas phase), the sulfur content is removed by the desulfurizer 6, and the liquid fuel. It is a mixed gas with the fuel gas vaporized by the vaporizer 8 (liquid fuel vaporized).

改質器２は、改質原料中の水蒸気及び燃料ガスを改質触媒で水蒸気改質反応させて、水素及び一酸化炭素を含有する改質ガスを生成する。水蒸気改質反応は非常に大きな吸熱反応であり、反応温度が５５０〜７５０℃程度と比較的高いので、高温の熱源が必要となる。そのため、ＳＯＦＣスタック３からの輻射熱を受熱することができる位置に改質器２が配置されたり、改質器２の近傍にオフガスバーナが設けられたりする。   The reformer 2 generates a reformed gas containing hydrogen and carbon monoxide by subjecting the steam and fuel gas in the reformed raw material to a steam reforming reaction using a reforming catalyst. The steam reforming reaction is a very large endothermic reaction, and since the reaction temperature is relatively high at about 550 to 750 ° C., a high-temperature heat source is required. Therefore, the reformer 2 is disposed at a position where the radiant heat from the SOFC stack 3 can be received, or an off-gas burner is provided in the vicinity of the reformer 2.

以上のように構成された燃料電池システム１の改質原料製造装置４においては、ＳＯＦＣスタック３から排出されたオフガスとの熱交換で液相状態の水Ｌを加熱して気化させる水気化器５内に、液体燃料から硫黄分を除去する脱硫器６が液相状態の水Ｌに浸漬されるように配置されている。そのため、水気化器５内に貯留された液相状態の水Ｌとの熱交換で液相状態の水Ｌの沸点近傍の温度に脱硫器６内の脱硫剤が加熱される。ここで、脱硫剤は、その脱硫能及び寿命の観点から、１００℃〜２００℃の温度に加熱されることが望ましい。そこで、水蒸気供給ライン１８に設けられたオリフィス７によって、例えば、水気化器５内の気相状態の水Ｖの圧力（水蒸気圧力）が０．４７ＭＰａとなるように調整されることで、水気化器５内の液相状態の水Ｌの沸点が１５０℃程度となる。これにより、脱硫器６内の脱硫剤を１００℃〜２００℃という適正な温度に容易且つ確実に維持することができ、液体燃料から硫黄分を十分に除去することが可能となる。   In the reforming raw material production apparatus 4 of the fuel cell system 1 configured as described above, the water vaporizer 5 that heats and vaporizes the liquid L water by heat exchange with the off-gas discharged from the SOFC stack 3. The desulfurizer 6 for removing sulfur from the liquid fuel is disposed so as to be immersed in the water L in the liquid phase state. Therefore, the desulfurization agent in the desulfurizer 6 is heated to a temperature near the boiling point of the water L in the liquid phase by heat exchange with the water L in the liquid phase stored in the water vaporizer 5. Here, it is desirable that the desulfurizing agent is heated to a temperature of 100 ° C. to 200 ° C. from the viewpoint of its desulfurization ability and life. Therefore, the water vaporization is performed by adjusting the pressure (water vapor pressure) of the water V in the vapor phase in the water vaporizer 5 to 0.47 MPa by the orifice 7 provided in the water vapor supply line 18, for example. The boiling point of the water L in the liquid phase in the vessel 5 is about 150 ° C. Thereby, the desulfurization agent in the desulfurizer 6 can be easily and reliably maintained at an appropriate temperature of 100 ° C. to 200 ° C., and the sulfur content can be sufficiently removed from the liquid fuel.

また、脱硫器６が水気化器５内に配置されているため、改質原料製造装置４、延いては燃料電池システム１の小型化を図ることができる。しかも、脱硫器６が水気化器５の底壁５ａに固定されているため、液相状態の水Ｌの液面が多少変化しても、脱硫器６が液相状態の水Ｌに確実に浸漬されるように容易に設計することができる。   Further, since the desulfurizer 6 is disposed in the water vaporizer 5, the reformed raw material production apparatus 4, and thus the fuel cell system 1 can be reduced in size. In addition, since the desulfurizer 6 is fixed to the bottom wall 5a of the water vaporizer 5, the desulfurizer 6 is surely changed into the liquid phase water L even if the liquid level of the liquid phase water L slightly changes. It can be easily designed to be immersed.

また、水気化器５においては、側壁５ｂに対して底壁５ａが着脱自在となっているため、例えば脱硫剤の寿命が尽きた際に、脱硫器６を水気化器５内から取り出して、新たな脱硫剤を有する脱硫器６に交換することができる。   Moreover, in the water vaporizer 5, since the bottom wall 5a is detachable with respect to the side wall 5b, for example, when the life of the desulfurizing agent is exhausted, the desulfurizer 6 is taken out from the water vaporizer 5, It can replace | exchange for the desulfurizer 6 which has a new desulfurization agent.

なお、水気化器５内の下側部分に、熱伝導性の高い材料からなる粒子を複数充填すれば、液相状態の水Ｌが気化する際に生じ易い突沸の発生箇所を分散させ、複数の突沸が同時に発生する確率も低減させて、突沸による蒸発振動の振幅を大幅に小さくすることができる。これにより、液相状態の水Ｌの液面の変動を抑制することが可能となる。このような効果を奏する粒子の材質は、温度及び雰囲気に耐え得る材料から適宜選ぶことができ、例えば、アルミナやシリカなどのセラミックス、或いはステンレス鋼等の金属を挙げることができる。また、粒子の形状としては、球、円柱、楔、直方体等、様々な形状を適宜採用することができる。
［第２の実施形態］ If the lower part in the water vaporizer 5 is filled with a plurality of particles made of a material having high thermal conductivity, the locations of bumping that are likely to occur when the water L in the liquid phase is vaporized are dispersed. The probability of simultaneous occurrence of bumping can be reduced, and the amplitude of evaporation vibration due to bumping can be greatly reduced. Thereby, it becomes possible to suppress the fluctuation | variation of the liquid level of the water L of a liquid phase state. The material of the particles exhibiting such an effect can be appropriately selected from materials that can withstand the temperature and atmosphere, and examples thereof include ceramics such as alumina and silica, and metals such as stainless steel. In addition, various shapes such as a sphere, a cylinder, a wedge, a rectangular parallelepiped, etc. can be appropriately employed as the particle shape.
[Second Embodiment]

図２は、本発明に係る燃料電池システムの第２の実施形態の構成図である。図２に示されるように、燃料電池システム１は、液体燃料導出部２３が水気化器５内において終端している点で、液体燃料導出部２３が水気化器５の天井壁５ｃを貫通している第１の実施形態の燃料電池システム１と主に相違している。以下、この相違点について詳細に説明する。   FIG. 2 is a configuration diagram of a second embodiment of the fuel cell system according to the present invention. As shown in FIG. 2, in the fuel cell system 1, the liquid fuel outlet 23 penetrates the ceiling wall 5 c of the water vaporizer 5 in that the liquid fuel outlet 23 terminates in the water vaporizer 5. This is mainly different from the fuel cell system 1 of the first embodiment. Hereinafter, this difference will be described in detail.

液相状態の水Ｌに浸漬されるように水気化器５内に配置され、水気化器５の底壁５ａに固定された脱硫器６の天井壁には、硫黄分が除去された液体燃料を脱硫器６外に導出するためのパイプ状の液体燃料導出部２３が設けられている。液体燃料導出部２３の一端は脱硫器６と接続されており、液体燃料導出部２３の他端は水気化器５内の上側部分（すなわち、気相状態の水Ｖが充満している領域）に開口している。脱硫器６によって硫黄分が除去された液体燃料を気化させる液体燃料気化器８は、液体燃料導出部２３に設けられている。   Liquid fuel from which sulfur content has been removed is disposed on the ceiling wall of the desulfurizer 6 which is disposed in the water vaporizer 5 so as to be immersed in the water L in the liquid phase and is fixed to the bottom wall 5a of the water vaporizer 5. A pipe-like liquid fuel lead-out portion 23 is provided for leading the fuel to the outside of the desulfurizer 6. One end of the liquid fuel lead-out part 23 is connected to the desulfurizer 6, and the other end of the liquid fuel lead-out part 23 is the upper part in the water vaporizer 5 (that is, a region filled with water V in the gas phase state). Is open. A liquid fuel vaporizer 8 that vaporizes the liquid fuel from which the sulfur content has been removed by the desulfurizer 6 is provided in the liquid fuel outlet 23.

このような構成により、水気化器５内の上側部分では、水気化器５によって気化させられた水蒸気（液相状態の水Ｌが気化させられたもの：気相状態の水Ｖ）と、脱硫器６によって硫黄分が除去され且つ液体燃料気化器８によって気化させられた燃料ガス（液体燃料が気化させられたもの）とが混合されて、その混合ガスである改質原料が製造される。   With such a configuration, in the upper part of the water vaporizer 5, the water vapor vaporized by the water vaporizer 5 (the water L in the liquid phase is vaporized: water V in the gas phase), and desulfurization The sulfur gas is removed by the vessel 6 and the fuel gas vaporized by the liquid fuel vaporizer 8 (the vaporized liquid fuel) is mixed to produce a reforming raw material that is the mixed gas.

水気化器５の側壁５ｂの上部には、改質原料を水気化器５外に導出するための改質原料導出部２６が設けられている。改質原料導出部２６は、改質原料供給ライン２５を介して改質器２と接続されている。水気化器５内の圧力を調整するオリフィス７は、改質原料供給ライン２５に設けられている。これにより、水気化器５内の上側部分で製造された改質原料は、改質原料供給ライン２５を介して改質器２に供給されることになる。   On the upper part of the side wall 5 b of the water vaporizer 5, a reformed material derivation unit 26 for leading the reformed material out of the water vaporizer 5 is provided. The reforming material lead-out unit 26 is connected to the reformer 2 via the reforming material supply line 25. An orifice 7 for adjusting the pressure in the water vaporizer 5 is provided in the reforming raw material supply line 25. As a result, the reforming raw material produced in the upper portion of the water vaporizer 5 is supplied to the reformer 2 via the reforming raw material supply line 25.

以上のように構成された燃料電池システム１の改質原料製造装置４によれば、第１の実施形態の燃料電池システム１の改質原料製造装置４と同様に、脱硫器６内の脱硫剤を適正な温度に容易且つ確実に維持することができ、液体燃料から硫黄分を十分に除去することが可能となる。   According to the reforming raw material manufacturing apparatus 4 of the fuel cell system 1 configured as described above, as in the reforming raw material manufacturing apparatus 4 of the fuel cell system 1 of the first embodiment, the desulfurizing agent in the desulfurizer 6. Can be easily and reliably maintained at an appropriate temperature, and the sulfur content can be sufficiently removed from the liquid fuel.

また、脱硫器６だけでなく液体燃料気化器８も水気化器５内に配置されているため、改質原料製造装置４、延いては燃料電池システム１のより一層の小型化を図ることができる。   Further, since not only the desulfurizer 6 but also the liquid fuel vaporizer 8 is disposed in the water vaporizer 5, it is possible to further reduce the size of the reforming raw material production apparatus 4, and thus the fuel cell system 1. it can.

また、水気化器５においては、側壁５ｂに対して底壁５ａが着脱自在となっており、更に、脱硫器６に設けられた液体燃料導出部２３が水気化器５内において終端しているため、例えば脱硫剤の寿命が尽きた際における脱硫器６の交換をより一層容易化することができる。   Further, in the water vaporizer 5, the bottom wall 5 a is detachable with respect to the side wall 5 b, and the liquid fuel lead-out portion 23 provided in the desulfurizer 6 terminates in the water vaporizer 5. Therefore, for example, when the life of the desulfurizing agent is exhausted, the replacement of the desulfurizer 6 can be further facilitated.

また、脱硫器６に設けられた液体燃料導出部２３が水気化器５内において終端していることから、液体燃料も加圧されるので、液体燃料が気化しない状態で液体燃料に対する脱硫を行うことができる。   Further, since the liquid fuel lead-out portion 23 provided in the desulfurizer 6 terminates in the water vaporizer 5, the liquid fuel is also pressurized, so that the liquid fuel is desulfurized without being vaporized. be able to.

本発明は、上述した第１及び第２の実施形態に限定されるものではない。   The present invention is not limited to the first and second embodiments described above.

例えば、上記各実施形態では、燃料電池スタックがＳＯＦＣスタックであったが、燃料電池スタックは、これに限定されず、固体高分子形燃料電池（Polymer Electrolyte Fuel Cell：ＰＥＦＣ）スタック等であってもよい。   For example, in each of the above embodiments, the fuel cell stack is an SOFC stack. However, the fuel cell stack is not limited to this, and may be a polymer electrolyte fuel cell (PEFC) stack or the like. Good.

また、上記各実施形態では、改質器が水蒸気改質するものであったが、改質器は、これに限定されず、部分酸化改質または自己熱改質（水蒸気改質と部分酸化改質との両者を行う）するものであってもよい。   Further, in each of the above embodiments, the reformer performs steam reforming. However, the reformer is not limited to this, and partial oxidation reforming or autothermal reforming (steam reforming and partial oxidation reforming). Do both with quality).

改質器から得られる改質ガスを、必要に応じてさらに処理することができる。例えば、一酸化炭素濃度を低減し水素濃度を高めるためのシフト反応（ＣＯ＋Ｈ2Ｏ→ＣＯ2＋Ｈ2）、一酸化炭素濃度低減のための選択酸化反応（２ＣＯ＋Ｏ2→２ＣＯ2）、加湿または除湿などの処理を行うことができる。従って、改質器から得られる水素含有ガスを用いて燃料電池により発電を行う場合、改質器から得られる改質ガスを直接燃料電池で用いてもよいし、改質ガスをシフト反応等の処理をした後に燃料電池で用いてもよい。 The reformed gas obtained from the reformer can be further processed as necessary. For example, a shift reaction (CO + H 2 O → CO 2 + H 2 ) for reducing the carbon monoxide concentration and increasing the hydrogen concentration, a selective oxidation reaction (2CO + O 2 → 2CO 2 ) for reducing the carbon monoxide concentration, humidification or dehumidification Etc. can be performed. Therefore, when power generation is performed by a fuel cell using a hydrogen-containing gas obtained from a reformer, the reformed gas obtained from the reformer may be used directly in the fuel cell, or the reformed gas may be used for a shift reaction or the like. You may use with a fuel cell after processing.

また、水気化器内の圧力を調整する圧力調整器は、オリフィスに限定されず、その他の絞り弁や、圧力調整可能な圧力調整弁等であってもよい。圧力調整器が圧力調整弁である場合には、燃料電池スタックから排出されるオフガスの熱量が変化して液相状態の水の液面が変化しそうになっても、オフガスの熱量に応じて水気化器内の圧力を調整することにより、脱硫器を液相状態の水に確実に浸漬させておくことができる。   Moreover, the pressure regulator for adjusting the pressure in the water vaporizer is not limited to the orifice, and may be another throttle valve, a pressure regulating valve capable of adjusting the pressure, or the like. When the pressure regulator is a pressure regulating valve, even if the amount of heat of off-gas discharged from the fuel cell stack changes and the liquid level of the liquid phase is likely to change, By adjusting the pressure in the chemical generator, the desulfurizer can be surely immersed in liquid phase water.

また、液体燃料気化器は、単なる空洞の容器であってもよいし、伝熱面積を確保するためのフィンをパイプの外面に複数設けたものであってもよい。   Further, the liquid fuel vaporizer may be a simple hollow container or may be provided with a plurality of fins for securing a heat transfer area on the outer surface of the pipe.

また、液相状態の水よりも気相状態の水のほうが高温であることから、液体燃料が気化しない状態で液体燃料に対して脱硫を行うためには、脱硫器が液相状態の水に浸漬されることが好ましいが、脱硫器内において液体燃料が気化しなければ、脱硫器の一部が気相状態の水に晒されてもよい。   In addition, since water in the gas phase is hotter than water in the liquid phase, in order to desulfurize the liquid fuel in a state where the liquid fuel does not vaporize, the desulfurizer converts the water in the liquid phase. It is preferable to be immersed, but if the liquid fuel does not vaporize in the desulfurizer, a part of the desulfurizer may be exposed to water in a gas phase.

また、脱硫に供する液体燃料は、脱硫器に導入する前に予熱してもよい。この予熱にもスタックから排出されるオフガスの熱量の一部を割り当ててもよい。また、高温で作動する固体酸化物形燃料電池では、筐体外壁に燃料供給ラインを張り巡らし、ＳＯＦＣスタックからの輻射熱の一部を割り当ててもよい。   Further, the liquid fuel to be used for desulfurization may be preheated before being introduced into the desulfurizer. You may allocate a part of calorie | heat amount of the off gas discharged | emitted from a stack also to this preheating. In a solid oxide fuel cell that operates at a high temperature, a fuel supply line may be provided around the outer wall of the housing, and a part of the radiant heat from the SOFC stack may be allocated.

本発明に係る燃料電池システムの第１の実施形態の構成図である。1 is a configuration diagram of a first embodiment of a fuel cell system according to the present invention. FIG. 本発明に係る燃料電池システムの第２の実施形態の構成図である。It is a block diagram of 2nd Embodiment of the fuel cell system which concerns on this invention.

符号の説明Explanation of symbols

１…燃料電池システム、２…改質器、３…固体酸化物形燃料電池（ＳＯＦＣ）スタック（燃料電池スタック）、４…改質原料製造装置、５…水気化器、６…脱硫器、７…オリフィス（圧力調整器）、８…液体燃料気化器。   DESCRIPTION OF SYMBOLS 1 ... Fuel cell system, 2 ... Reformer, 3 ... Solid oxide fuel cell (SOFC) stack (fuel cell stack), 4 ... Reformed raw material manufacturing apparatus, 5 ... Water vaporizer, 6 ... Desulfurizer, 7 ... orifice (pressure regulator), 8 ... liquid fuel vaporizer.

Claims (3)

水素を含有する改質ガスを生成する改質器に供給される改質原料を製造する改質原料製造装置であって、
前記改質原料となる水を気化させる水気化器と、
前記水気化器内に配置され、前記改質原料となる液体燃料から硫黄分を除去する脱硫器と、
前記水気化器内の圧力を調整する圧力調整器と、を備えることを特徴とする改質原料製造装置。 A reforming material production apparatus for producing a reforming material to be supplied to a reformer that generates reformed gas containing hydrogen,
A water vaporizer for vaporizing water as the reforming raw material;
A desulfurizer that is disposed in the water vaporizer and removes sulfur from the liquid fuel that is the reforming raw material;
And a pressure regulator for regulating the pressure in the water vaporizer. 前記水気化器内には、前記脱硫器によって前記硫黄分が除去された前記液体燃料を気化させる液体燃料気化器が配置されており、
前記水気化器によって気化させられた前記水と前記液体燃料気化器によって気化させられた前記液体燃料とは、前記水気化器内おいて混合されて前記改質原料とされることを特徴とする請求項１記載の改質原料製造装置。 A liquid fuel vaporizer that vaporizes the liquid fuel from which the sulfur content has been removed by the desulfurizer is disposed in the water vaporizer,
The water vaporized by the water vaporizer and the liquid fuel vaporized by the liquid fuel vaporizer are mixed in the water vaporizer to become the reforming raw material. The reforming raw material manufacturing apparatus according to claim 1. 請求項１又は２記載の改質原料製造装置と、
前記改質原料製造装置によって製造された改質原料を用いて改質ガスを生成する改質器と、
前記改質器によって生成された前記改質ガスを用いて発電を行う燃料電池スタックと、を備えることを特徴とする燃料電池システム。 The reforming raw material production apparatus according to claim 1 or 2,
A reformer that generates a reformed gas using the reformed material produced by the reformed material production apparatus;
And a fuel cell stack that generates electric power using the reformed gas generated by the reformer.
JP2007282107A 2007-10-30 2007-10-30 Reformed raw material manufacturing apparatus and fuel cell system Expired - Fee Related JP5129544B2 (en)

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PCT/JP2008/069663 WO2009057648A1 (en) 2007-10-30 2008-10-29 Apparatus for producing reforming raw material and fuel cell system
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US11542159B2 (en) 2020-06-22 2023-01-03 Saudi Arabian Oil Company Autothermal reformer system with liquid desulfurizer for SOFC system
US11618003B2 (en) 2020-06-23 2023-04-04 Saudi Arabian Oil Company Diesel reforming apparatus having a heat exchanger for higher efficiency steam reforming for solid oxide fuel cells (SOFC)

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