JP2002252018A - Operation controlling method of reforming equipment for fuel cell - Google Patents

Operation controlling method of reforming equipment for fuel cell

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Publication number
JP2002252018A
JP2002252018A JP2001050704A JP2001050704A JP2002252018A JP 2002252018 A JP2002252018 A JP 2002252018A JP 2001050704 A JP2001050704 A JP 2001050704A JP 2001050704 A JP2001050704 A JP 2001050704A JP 2002252018 A JP2002252018 A JP 2002252018A
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JP
Japan
Prior art keywords
fuel cell
section
temperature
reforming
reformer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2001050704A
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Japanese (ja)
Other versions
JP2002252018A5 (en
JP4110354B2 (en
Inventor
Takashi Ishikawa
貴史 石川
Shigenori Onuma
重徳 尾沼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aisin Corp
Original Assignee
Aisin Seiki Co Ltd
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Filing date
Publication date
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Priority to JP2001050704A priority Critical patent/JP4110354B2/en
Publication of JP2002252018A publication Critical patent/JP2002252018A/en
Publication of JP2002252018A5 publication Critical patent/JP2002252018A5/ja
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Publication of JP4110354B2 publication Critical patent/JP4110354B2/en
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Classifications

    • 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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  • Fuel Cell (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

PROBLEM TO BE SOLVED: To prevent aggravation of partial load efficiency and to prevent fall of catalyst activity by making an expensive CO sensor unnecessary and making presumption and guarantee of CO concentration at the time of starting ensure. SOLUTION: At the time of starting, operation control is performed by presuming reform composition from an exit temperature (Tc1) of the above reform part 2, a catalyst temperature (Tc2) of the above CO shift part 5, and a catalyst temperature (Tc3) of the above CO selective oxidization part 6. Therefore, the CO sensor in the operation control at the time of starting in the former is made unnecessary.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、燃料電池用の水蒸
気改質器を備えた燃料電池用改質装置において、改質部
の出口温度とシフト部の触媒温度とＣＯ選択酸化部の触
媒温度に基づき改質組成を推定することにより、起動時
における運転を制御するようにした燃料電池用改質装置
の運転制御方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reformer for a fuel cell having a steam reformer for a fuel cell, and more particularly to an outlet temperature of a reforming section, a catalyst temperature of a shift section, and a catalyst temperature of a CO selective oxidizing section. The present invention relates to an operation control method for a fuel cell reformer in which the operation at the time of startup is controlled by estimating a reforming composition based on a fuel cell.

【０００２】[0002]

【従来の技術】従来の固体高分子型燃料電池による発電
システムを構築する場合、固体高分子型燃料電池に導入
される燃料ガス中の一酸化炭素濃度は１０ｐｐｍ以下と
する必要がある。一方でメタン等の炭化水素から水素を
取り出す場合、副生成物として一酸化炭素が以下の化１
および化２に従い生成される。2. Description of the Related Art When constructing a power generation system using a conventional polymer electrolyte fuel cell, the concentration of carbon monoxide in fuel gas introduced into the polymer electrolyte fuel cell must be 10 ppm or less. On the other hand, when hydrogen is extracted from hydrocarbons such as methane, carbon monoxide is a by-product of the following chemical formula 1.
And is generated according to Formula 2.

【化１】 Embedded image

【化２】 Embedded image

【０００３】上記化１および化２における組成は、温度
平衡状態により決定され、一般的にＣＯは０．３〜１％
程度となる。そこでＣＯを化３により低減する。The composition in the above chemical formulas (1) and (2) is determined by the temperature equilibrium state.
About. Therefore, CO is reduced by Chemical Formula 3.

【化３】 Embedded image

【０００４】上記化１および化２において生成されるＣ
Ｏ量と、化３において吸込むＯ2 量により最終的なＣＯ
濃度が決定されるが、実際のシステムで１０ｐｐｍ以下
を保証することが重要である。The C produced in the above chemical formulas 1 and 2
The final amount of CO depends on the amount of O and the amount of O2
Although the concentration is determined, it is important to guarantee less than 10 ppm in a practical system.

【０００５】従来の第１の燃料電池発電システム（特開
平８−３０６３７８）においては、ＣＯセンサによる検
出を試みていた。In the first conventional fuel cell power generation system (JP-A-8-306378), detection by a CO sensor has been attempted.

【０００６】また従来の第２の燃料電池発電システム
（特開２０００−６７８９７）においては、被改質ガス
流量、吸込み酸素量を一定とすることでシステムの安定
化を試みていた。Further, in the second conventional fuel cell power generation system (JP-A-2000-67897), an attempt was made to stabilize the system by keeping the flow rate of the gas to be reformed and the amount of oxygen absorbed.

【０００７】[0007]

【発明が解決しようとする課題】上記従来の第１の燃料
電池発電システムにおける前記ＣＯセンサは、特に水素
ガス雰囲気においては高価であり且つ、大掛かりな物と
なり実用的ではないという問題があった。However, the CO sensor in the first conventional fuel cell power generation system has a problem that it is expensive and large-scale, especially in a hydrogen gas atmosphere, and is not practical.

【０００８】また上記従来の第２の燃料電池発電システ
ムにおいては、起動時におけるＣＯ濃度の推定および保
証方法が不確かであり、また部分負荷効率が悪くなると
いう問題があった。Further, in the above-mentioned conventional second fuel cell power generation system, there is a problem that the method of estimating and guaranteeing the CO concentration at the time of startup is uncertain, and the partial load efficiency deteriorates.

【０００９】さらに上記従来の燃料電池発電システムに
おいては、選択酸化部の温度が低い状態で、酸化剤を吹
き込むと水素が燃焼して生成される水が凝縮し、触媒表
面に付着して触媒活性が妨げられるという問題点があっ
た。Further, in the above conventional fuel cell power generation system, when the oxidizing agent is blown in a state where the temperature of the selective oxidizing section is low, water generated by burning of hydrogen is condensed and adheres to the surface of the catalyst to cause catalytic activity. There was a problem that was hindered.

【００１０】そこで本発明者は、燃料電池用の水蒸気改
質器を備えた燃料電池用改質装置において、改質部の出
口温度とシフト部の触媒温度とＣＯ選択酸化部の触媒温
度に基づき改質組成を推定することにより、起動時にお
ける運転を制御するようにするという本発明の技術的思
想に着眼し、更に研究開発を重ねた結果、高価なＣＯセ
ンサを不要にし、起動時におけるＣＯ濃度の推定および
保証を確実にして、部分負荷効率の悪化を防止し、触媒
活性の低下を防止するという目的を達成する本発明に到
達した。Therefore, the present inventor has proposed a fuel cell reformer having a fuel cell steam reformer based on the outlet temperature of the reforming section, the catalyst temperature of the shift section, and the catalyst temperature of the CO selective oxidizing section. Focusing on the technical idea of the present invention to control the operation at the time of start-up by estimating the reforming composition, as a result of further research and development, an expensive CO sensor became unnecessary, The present invention has been achieved which achieves the object of ensuring the estimation and guarantee of the concentration, preventing the deterioration of the partial load efficiency, and preventing the reduction of the catalyst activity.

【００１１】[0011]

【課題を解決するための手段】本発明（請求項１に記載
の第１発明）の燃料電池用改質装置の運転制御方法は、
燃料電池用の水蒸気改質器を備えた燃料電池用改質装置
において、改質部の出口温度とシフト部の触媒温度とＣ
Ｏ選択酸化部の触媒温度に基づき改質組成を推定するこ
とにより、起動時における運転を制御するようにしたも
のである。According to a first aspect of the present invention, there is provided a method for controlling the operation of a reformer for a fuel cell, comprising the steps of:
In a reformer for a fuel cell equipped with a steam reformer for a fuel cell, an outlet temperature of a reforming section, a catalyst temperature of a shift section, and C
The operation at the time of startup is controlled by estimating the reforming composition based on the catalyst temperature of the O selective oxidizing section.

【００１２】本発明（請求項２に記載の第２発明）の燃
料電池用改質装置の運転制御方法は、前記第１発明にお
いて、前記ＣＯ選択酸化部の触媒温度に従って該ＣＯ選
択酸化部に供給するＣＯ酸化剤の量を制御することによ
り、起動時における運転を制御するようにしたものであ
る。According to a second aspect of the present invention, there is provided the operation control method for the reformer for a fuel cell according to the first aspect of the present invention, wherein the CO selective oxidizing section is controlled according to a catalyst temperature of the CO selective oxidizing section. The operation at startup is controlled by controlling the amount of CO oxidant to be supplied.

【００１３】本発明（請求項３に記載の第３発明）の燃
料電池用改質装置の運転制御方法は、前記第２発明にお
いて、前記改質部の出口温度を一定範囲内に保持すると
ともに、前記シフト部の触媒温度に従って前記ＣＯ選択
酸化部に供給するＣＯ酸化剤の量を制御することによ
り、定常時における運転を制御するようにしたものであ
る。According to a third aspect of the present invention, there is provided the operation control method for the fuel cell reforming apparatus, wherein the outlet temperature of the reforming section is maintained within a predetermined range in the second aspect. The steady-state operation is controlled by controlling the amount of the CO oxidizing agent supplied to the CO selective oxidizing unit according to the catalyst temperature of the shift unit.

【００１４】本発明（請求項４に記載の第４発明）の燃
料電池用改質装置の運転制御方法は、前記第３発明にお
いて、負荷変動時に前記改質部の出口温度を一定範囲内
に保持するように運転を制御するようにしたものであ
る。According to a fourth aspect of the present invention, there is provided the operation control method of the reforming apparatus for a fuel cell according to the third aspect, wherein the outlet temperature of the reforming section is kept within a certain range when the load changes. The operation is controlled so as to be maintained.

【００１５】本発明（請求項５に記載の第５発明）の燃
料電池用改質装置の運転制御方法は、前記第４発明にお
いて、負荷が増加する場合は、水または水蒸気の供給量
および前記ＣＯ選択酸化部に供給するＣＯ酸化剤の量を
先行して増加することにより、負荷変動時における運転
を制御するようにしたものである。The operation control method for a reformer for a fuel cell according to the present invention (fifth invention according to claim 5) is characterized in that, in the fourth invention, when the load increases, the supply amount of water or steam and the The operation at the time of load change is controlled by increasing the amount of the CO oxidizing agent supplied to the CO selective oxidizing section in advance.

【００１６】本発明（請求項６に記載の第６発明）の燃
料電池用改質装置の運転制御方法は、前記第５発明にお
いて、負荷が減少する場合は、改質原料流量を先行して
減少することにより、負荷変動時における運転を制御す
るようにしたものである。In the operation control method for a reformer for a fuel cell according to the present invention (a sixth invention according to claim 6), in the fifth invention, when the load is reduced, the flow rate of the reforming raw material is preceded. By decreasing, the operation at the time of load change is controlled.

【００１７】[0017]

【発明の作用および効果】上記構成より成る第１発明の
燃料電池用改質装置の運転制御方法は、燃料電池用の水
蒸気改質器を備えた燃料電池用改質装置において、改質
部の出口温度とシフト部の触媒温度とＣＯ選択酸化部の
触媒温度に基づき改質組成を推定することにより、起動
時における運転を制御するようにしたので、高価なＣＯ
センサを不要にするという効果を奏する。According to the first aspect of the present invention, there is provided a fuel cell reforming apparatus having a steam reformer for a fuel cell. By estimating the reforming composition based on the outlet temperature, the catalyst temperature of the shift section, and the catalyst temperature of the CO selective oxidizing section, the operation at the time of startup is controlled.
This has the effect of eliminating the need for a sensor.

【００１８】上記構成より成る第２発明の燃料電池用改
質装置の運転制御方法は、前記第１発明において、前記
ＣＯ選択酸化部の触媒温度に従って該ＣＯ選択酸化部に
供給するＣＯ酸化剤の量を制御することにより、起動時
における運転を制御するようにしたので、触媒への水分
付着および触媒活性の低下を防止するという効果を奏す
る。According to a second aspect of the present invention, there is provided the operation control method of the reformer for a fuel cell according to the first aspect, wherein the CO oxidizer supplied to the CO selective oxidizing section according to the catalyst temperature of the CO selective oxidizing section. Since the operation at the time of startup is controlled by controlling the amount, there is an effect that the adhesion of water to the catalyst and the decrease in catalytic activity are prevented.

【００１９】上記構成より成る第３発明の燃料電池用改
質装置の運転制御方法は、前記第２発明において、前記
改質部の出口温度を一定範囲内に保持するとともに、前
記シフト部の触媒温度に従って前記ＣＯ選択酸化部に供
給するＣＯ酸化剤の量を制御することにより、定常時に
おける運転を制御するようにしたので、定常時における
運転制御を可能にするという効果を奏する。According to the third aspect of the present invention, there is provided the operation control method for the fuel cell reforming apparatus according to the second aspect of the present invention, wherein the outlet temperature of the reforming section is maintained within a predetermined range and the catalyst of the shift section is controlled. The steady-state operation is controlled by controlling the amount of the CO oxidant supplied to the CO selective oxidizing unit according to the temperature, so that the effect of enabling the steady-state operation control is achieved.

【００２０】上記構成より成る第４発明の燃料電池用改
質装置の運転制御方法は、前記第３発明において、負荷
変動時に前記改質部の出口温度を一定範囲内に保持する
ように運転を制御するようにしたので、負荷変動時にお
けるＣＯの上昇の抑制を可能にするという効果を奏す
る。According to a fourth aspect of the present invention, there is provided the operation control method for a fuel cell reforming apparatus according to the third aspect, wherein the operation is performed such that the outlet temperature of the reforming section is maintained within a certain range when the load changes. Since the control is performed, it is possible to suppress an increase in CO during a load change.

【００２１】上記構成より成る第５発明の燃料電池用改
質装置の運転制御方法は、前記第４発明において、負荷
が増加する場合は、水または水蒸気の供給量および前記
ＣＯ選択酸化部に供給するＣＯ酸化剤の量を先行して増
加することにより、負荷変動時における運転を制御する
ようにしたので、負荷変動時におけるＣＯの上昇を抑制
するという効果を奏する。According to the fifth aspect of the present invention, there is provided an operation control method for a fuel cell reformer according to the fourth aspect of the present invention, wherein when the load increases, the supply amount of water or steam and the supply amount to the CO selective oxidizing section are increased. The operation at the time of load change is controlled by increasing the amount of the CO oxidizer to be performed in advance, so that an effect of suppressing an increase in CO at the time of load change is exerted.

【００２２】上記構成より成る第６発明の燃料電池用改
質装置の運転制御方法は、前記第５発明において、負荷
が減少する場合は、改質原料流量を先行して減少するこ
とにより、負荷変動時における運転を制御するようにし
たので、負荷変動時におけるＣＯの上昇を抑制するとい
う効果を奏する。The operation control method for a fuel cell reforming apparatus according to the sixth aspect of the present invention, which is configured as described above, is characterized in that, when the load decreases in the fifth aspect of the invention, the flow rate of the reforming raw material is reduced first. Since the operation at the time of the change is controlled, an effect of suppressing the rise of CO at the time of the load change is exerted.

【００２３】[0023]

【発明の実施の形態】以下本発明の実施の形態につき、
図面を用いて説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described.
This will be described with reference to the drawings.

【００２４】（実施形態）本実施形態の燃料電池用改質
装置の運転制御方法について、図１ないし図８を用いて
以下に説明する。(Embodiment) An operation control method of a reformer for a fuel cell according to this embodiment will be described below with reference to FIGS.

【００２５】本実施形態の燃料電池用改質装置は、図１
に示されるように水蒸気改質器における蒸発部としての
蒸発器３の温度（Ｔｃ０）、改質部２の出口温度（ＴＣ
１）、ＣＯシフト部５の触媒温度（Ｔｃ２）、ＣＯ選択
酸化部６の触媒温度（Ｔｃ３）、前記改質部２の壁面温
度（Ｔｃｗ）を検出する手段を備え、下記のような運転
制御方法を用いる。The reformer for a fuel cell according to this embodiment is shown in FIG.
As shown in the figure, the temperature of the evaporator 3 as an evaporator in the steam reformer (Tc0), the outlet temperature of the reformer 2 (TC
1) a means for detecting the catalyst temperature (Tc2) of the CO shift unit 5, the catalyst temperature (Tc3) of the CO selective oxidation unit 6, and the wall surface temperature (Tcw) of the reforming unit 2; Method.

【００２６】起動時においては、前記改質部２の出口温
度（ＴＣ１）、前記ＣＯシフト部５の触媒温度（Ｔｃ
２）および前記ＣＯ選択酸化部６の触媒温度（Ｔｃ３）
から改質組成を推定して、運転制御を行うものであり、
従来における起動時の運転制御におけるＣＯセンサを不
要にするものである。At the time of startup, the outlet temperature (TC1) of the reforming section 2 and the catalyst temperature (Tc) of the CO shift section 5
2) and the catalyst temperature (Tc3) of the CO selective oxidation section 6
Estimate the reforming composition from, to perform operation control,
This eliminates the need for a CO sensor in the conventional operation control at startup.

【００２７】また前記ＣＯ選択酸化部６の触媒温度（Ｔ
ｃ３）に従って前記ＣＯ選択酸化部６に供給するＣＯ酸
化剤としての空気の供給量をコントロールするものであ
り、触媒への水分付着および触媒活性の低下すなわち
（失活）を防止するものである。The catalyst temperature of the CO selective oxidation section 6 (T
In accordance with c3), the amount of air supplied as a CO oxidant to be supplied to the CO selective oxidizing section 6 is controlled to prevent adhesion of water to the catalyst and a decrease in catalytic activity, ie, (deactivation).

【００２８】また定常時においては、前記改質部２の出
口温度（ＴＣ１）を一定範囲内に保持するとともに、前
記ＣＯシフト部５の触媒温度（Ｔｃ２）に従って前記Ｃ
Ｏ選択酸化部６に供給するＣＯ酸化剤（ＣＯ酸化材）の
空気流量をコントロールすることにより、定常時におけ
る運転制御を可能にするものである。In a steady state, the outlet temperature (TC1) of the reforming section 2 is maintained within a certain range, and the C (C1) is controlled in accordance with the catalyst temperature (Tc2) of the CO shift section 5.
By controlling the air flow rate of the CO oxidizing agent (CO oxidizing material) supplied to the O selective oxidizing section 6, it is possible to control the operation in a steady state.

【００２９】負荷変動時においては、前記改質部２の出
口温度（ＴＣ１）を一定範囲内に保持するとともに、負
荷増加時においては水（水蒸気）の供給量と酸化剤量を
先行して増加制御するものであり、負荷減少時において
は改質原料流量を先行して減少制御するものである。When the load fluctuates, the outlet temperature (TC1) of the reforming section 2 is maintained within a certain range, and when the load increases, the supply amount of water (steam) and the oxidizer amount are increased first. When the load is reduced, the flow rate of the reforming raw material is controlled in advance.

【００３０】本実施形態の水蒸気改質装置においては、
前記改質部２で化１（−Ｑ1 ：吸熱）および化２（＋Ｑ
2 ：発熱）、前記ＣＯシフト部５で化２、前記ＣＯ選択
酸化部６において化３（＋Ｑ3 ：発熱）の反応が進行す
る。In the steam reformer of the present embodiment,
In the reforming section 2, chemical formula 1 (-Q1: endothermic) and chemical formula 2 (+ Q
2: exothermic), the reaction of chemical formula 2 (+ Q3: exothermic) proceeds in the CO shift section 5 and chemical formula 3 (+ Q3: exothermic) in the CO selective oxidation section 6.

【００３１】上記化１および化２は、平衡反応のため、
圧力一定の条件下では前記改質部２の温度と前記ＣＯシ
フト部５の温度により、ＣＯ濃度と他の化学種の組成が
決定される。The above chemical formulas (1) and (2) are used for an equilibrium reaction.
Under a constant pressure condition, the CO concentration and the composition of other chemical species are determined by the temperature of the reforming section 2 and the temperature of the CO shift section 5.

【００３２】改質温度７００℃と６５０℃の場合につい
て、シフト温度の変化に伴う改質ガス中の平衡ＣＯ濃度
の変化を理論的に計算すると下記の様になる。改質原料
は燃焼用１３Ａガスおよび供給スチームと改質原料の比
を示すＳ／Ｃ＝３として計算を行った。For the cases where the reforming temperatures are 700 ° C. and 650 ° C., the change in the equilibrium CO concentration in the reformed gas accompanying the change in the shift temperature is calculated as follows. The calculation was performed on the assumption that the reforming raw material was S / C = 3, which indicates the ratio of 13A gas for combustion and the supply steam to the reforming raw material.

【００３３】平衡濃度を示す図２から分かるように、Ｃ
Ｏ濃度はシフト温度に強く依存する。前記改質部２への
依存性も無視できないレベルであるが、実際の運転では
後述する具体例で示すように前記改質部２の温度が制御
可能であるから、実システムにおいてはシフト温度から
ＣＯ温度を推定することが可能である。As can be seen from FIG.
O concentration strongly depends on the shift temperature. Although the dependence on the reforming unit 2 is not negligible, in an actual operation, the temperature of the reforming unit 2 can be controlled as shown in a specific example described later. It is possible to estimate the CO temperature.

【００３４】これらの事を確認するために、実機試験に
おいて、前記ＣＯシフト部５の温度を意図的に加熱およ
び冷却し、平衡濃度と実験データの比較を行ったことろ
図３に示される結果が得られた。In order to confirm these facts, in the actual machine test, the temperature of the CO shift section 5 was intentionally heated and cooled, and the equilibrium concentration was compared with the experimental data. was gotten.

【００３５】試験データの温度として前記ＣＯシフト部
５の触媒の出口近傍の温度を用いている。このように、
平衡濃度と実機データの間には相関が認められ、シフト
触媒の温度を用いてＣＯ濃度の推定が可能であることが
確認できた。The temperature in the vicinity of the catalyst outlet of the CO shift unit 5 is used as the temperature of the test data. in this way,
A correlation was found between the equilibrium concentration and the actual machine data, and it was confirmed that the CO concentration could be estimated using the temperature of the shift catalyst.

【００３６】平衡値と実験データ比較が示される図３に
おいて、ここで前提となることは、前記ＣＯシフト部５
の触媒量が、平衡濃度近くまで達するのに十分な空間
（触媒量）が必要である。In FIG. 3 showing the comparison between the equilibrium value and the experimental data, it is assumed that the CO shift unit 5 is used.
A sufficient amount of space (catalyst amount) is required so that the amount of the catalyst reaches near the equilibrium concentration.

【００３７】シフト触媒に銅・亜鉛系の触媒を用いた場
合、前記ＣＯシフト部５の単体試験でＳＶ値が（空間速
度）３５００ＨＲ-1であれば、平衡濃度近くまでＣＯ濃
度が低減することを確認しているが、触媒の劣化、実シ
ステムでは温度条件が一定で無いことから単体試験とは
触媒活性に差異が生じることを考慮にいれ、後述の具体
例ではＳＶ＝７５０をねらいとして前記ＣＯシフト部５
の設計・製作を行った。When a copper / zinc-based catalyst is used as the shift catalyst, if the SV value (space velocity) is 3500 HR -1 in a unit test of the CO shift unit 5, the CO concentration is reduced to near the equilibrium concentration. However, taking into account the deterioration of the catalyst and the fact that the temperature conditions are not constant in the actual system, a difference occurs in the catalyst activity from the unit test, and in the specific example described later, SV = 750 was aimed at. CO shift unit 5
Was designed and manufactured.

【００３８】また、負荷変動時に急激な流量変化を行う
と、バルブ操作に伴う圧力変動と蒸発部における上記発
生量の遅れが生じ、ある瞬間において仮定した平衡濃度
からのズレが生じることが予想される。Further, if a rapid change in the flow rate occurs at the time of a load change, a pressure change accompanying the valve operation and a delay of the above-mentioned generated amount in the evaporating section occur, and a deviation from the assumed equilibrium concentration at a certain moment is expected. You.

【００３９】図４においては、改質器の負荷を５０％か
ら１００％に負荷変動させた場合のシフト部出口のＣＯ
濃度を示す。このとき、改質原料（１３Ａ）の流量と改
質水は、ほぼ同時に５０％〜１００％相当量まで増加さ
せた。また、計測の関係でＣＯ濃度の変化は実際の状態
よりもやや遅れて記録されている。In FIG. 4, when the load of the reformer is changed from 50% to 100%, the CO
Indicates the concentration. At this time, the flow rate of the reforming raw material (13A) and the reforming water were increased almost at the same time to an amount equivalent to 50% to 100%. Also, due to the measurement, the change in the CO concentration is recorded slightly later than the actual state.

【００４０】負荷増加時のＣＯ濃度が示される図４にお
いて、予想された様に、負荷変動時に改質ガス中のＣＯ
濃度が一時的に上昇していることが確認できる。このよ
うなＣＯの変動量を前記ＣＯ選択酸化部６で吸収するた
めには酸化剤量をコントロールする必要があるが、従来
のようにＣＯセンサを用いない場合、負荷変動時にどの
程度のＣＯが発生するか予想するのが困難である。In FIG. 4 showing the CO concentration when the load is increased, as expected, the CO in the reformed gas when the load fluctuates is changed.
It can be confirmed that the concentration temporarily increased. It is necessary to control the amount of the oxidizing agent in order to absorb such a fluctuation amount of CO in the CO selective oxidizing section 6. However, when a CO sensor is not used as in the related art, how much CO does It is difficult to predict what will happen.

【００４１】また、ＣＯを酸化除去する場合、当量比３
以上の酸化剤を供給することが一般的である。そのた
め、大量のＣＯを除去すると水素も大量に燃焼し大きな
熱発生がある。ＣＯ選択酸化触媒には活性温度閾値があ
るので、これらの発熱を除去する必要があるが、定常時
にくらべて、負荷変動時の発熱は数倍になるために、大
きな冷却能力が必要になる。When CO is removed by oxidation, the equivalent ratio is 3
It is common to supply the above oxidizing agent. Therefore, when a large amount of CO is removed, a large amount of hydrogen is combusted and large heat is generated. Since the CO selective oxidation catalyst has an activation temperature threshold value, it is necessary to remove these heats. However, heat generation at the time of a load change becomes several times larger than that at the time of steady state, so that a large cooling capacity is required.

【００４２】一方で定常時に冷却が過ぎると触媒温度が
活性以下に下がる可能性がある。従って、前記ＣＯ選択
酸化部６の冷却構造は幅広い範囲での冷却コントロール
が要求され、複雑なシステムになってしまう。On the other hand, if the cooling is excessive during the steady state, the catalyst temperature may drop below the activity. Therefore, the cooling structure of the CO selective oxidizing unit 6 requires a wide range of cooling control, resulting in a complicated system.

【００４３】ところで上記化１および化２で決定される
平衡組成は水蒸気量にも依存する。そこで、Ｓ／Ｃを変
化させた時の平衡濃度を図５に示されるように計算し
た。このようにＳ／Ｃを高くすることでＣＯ濃度を下げ
られることが分かる。The equilibrium composition determined by the above chemical formulas 1 and 2 also depends on the amount of water vapor. Therefore, the equilibrium concentration when the S / C was changed was calculated as shown in FIG. It can be seen that the CO concentration can be reduced by increasing the S / C as described above.

【００４４】水蒸気量の影響による平衡濃度が示される
図５において、前記改質部２においては６８０℃であ
り、前記ＣＯシフト部５においては２００℃である。In FIG. 5 showing the equilibrium concentration due to the influence of the amount of water vapor, the temperature is 680 ° C. in the reforming section 2 and 200 ° C. in the CO shift section 5.

【００４５】そこで、次のような試験を試みた。負荷変
動時に （ａ） 水供給量（水蒸気量）を改質原料より先行で増
加させる。 （ｂ） Ｔ分間のタイムラグの後にＣＯ選択酸化用酸化
剤を増加させ、ただちに改質原料流量を増加させる。上
記方法により、タイムラグＴ＝１．５、３、５分の場合
について前記ＣＯシフト部５の出口におけるＣＯ濃度を
調べた。いずれの場合も前記ＣＯ選択酸化部６における
ＣＯ濃度の上昇は認められなかった。Therefore, the following test was attempted. When the load fluctuates: (a) The water supply amount (steam amount) is increased before the reforming raw material. (B) After the time lag of T minutes, the oxidizing agent for selective oxidation of CO is increased, and the reforming material flow rate is immediately increased. According to the above method, the CO concentration at the outlet of the CO shift unit 5 was examined for the time lag T = 1.5, 3, 5 minutes. In any case, no increase in the CO concentration in the CO selective oxidation section 6 was observed.

【００４６】これらの結果がタイムラグ１．５分の場合
は図６、タイムラグ３分の場合は図７、タイムラグ５分
の場合は図８に示される。このように、改質原料に先だ
って水蒸気を先行増加させることで負荷変動時にＣＯの
上昇は抑制され、タイムラグ３分の場合（図７）におけ
る前記ＣＯシフト部５の出口におけるＣＯ濃度の上昇は
ほとんど無いことが分かる。つまりＴ＝３分とすること
で、本実施形態の一つである前記ＣＯシフト部５の温度
Ｔｃ２からマップを用いて、ＣＯ選択酸化剤流量を制御
が有効に働くことが確認できた。FIG. 6 shows the results when the time lag is 1.5 minutes, FIG. 7 shows the results when the time lag is 3 minutes, and FIG. 8 shows the results when the time lag is 5 minutes. As described above, by increasing the water vapor prior to the reforming raw material, the increase in CO at the time of load change is suppressed, and the increase in the CO concentration at the outlet of the CO shift unit 5 in the case of a time lag of 3 minutes (FIG. 7) is almost zero It turns out that there is no. That is, by setting T = 3 minutes, it was confirmed that the control of the flow rate of the CO selective oxidant works effectively using the map from the temperature Tc2 of the CO shift unit 5, which is one of the present embodiments.

【００４７】定置用の発電システムを考える場合、急峻
な負荷変動への追従は要求されないことが多いため、３
分以内における負荷変動能力があれば、実用上問題の無
い範囲と考えられる。When considering a stationary power generation system, it is often not required to follow a steep load change.
If there is a load variation capability within minutes, it is considered that there is no practical problem.

【００４８】[0048]

【発明の実施例】以下本発明の実施例につき、図面を用
いて説明する。Embodiments of the present invention will be described below with reference to the drawings.

【００４９】（実施例）本実施例の燃料電池用改質装置
の運転制御方法について、図１、図９、図１１ないし図
１５を用いて以下に説明する。(Embodiment) An operation control method of the reformer for a fuel cell according to this embodiment will be described below with reference to FIGS. 1, 9, and 11 to 15.

【００５０】本実施例の天然ガス用水蒸気改質器は、図
１に説明されるように燃焼バーナ１と、ルテニウム触媒
を用いた改質部２と、蒸発器３と、熱交換器４と、銅・
亜鉛系触媒を用いたＣＯシフト部５と、ルテニウム触媒
を用いたＣＯ選択酸化部６とから成る。As shown in FIG. 1, the natural gas steam reformer of this embodiment includes a combustion burner 1, a reforming section 2 using a ruthenium catalyst, an evaporator 3, and a heat exchanger 4. ,copper·
It comprises a CO shift section 5 using a zinc-based catalyst and a CO selective oxidation section 6 using a ruthenium catalyst.

【００５１】改質原料となる天然ガス（１３Ａ主成分メ
タン）は、前記蒸発部３で生成される蒸気と混合し、前
記熱交換器４で約５００℃前後まで予熱された後に前記
改質部２に導入され、燃焼バーナ１において加熱されな
がら、主に上述した化１によって示される改質主反応お
よび化２によって示される副反応であるシフト反応が起
こされる。[0051] Natural gas (13A main component methane) as a reforming raw material is mixed with steam generated in the evaporating section 3 and preheated to about 500 ° C. in the heat exchanger 4 before the reforming section. 2, while being heated in the combustion burner 1, a shift reaction, which is a main reforming reaction represented by Chemical Formula 1 and a side reaction represented by Chemical Formula 2, occurs.

【００５２】このとき改質ガス出口温度が６５０℃前後
（Ｔｅ）となるように前記燃焼バーナ１の燃焼量を調整
する。前記改質部２を出たガスは前記熱交換器４におい
て原料ガスと熱交換を行い、１７０〜２５０℃程度まで
冷却された後に前記ＣＯシフト部５において化２によっ
て示されるシフト反応が起こされる。At this time, the combustion amount of the combustion burner 1 is adjusted so that the outlet temperature of the reformed gas is about 650 ° C. (Te). The gas leaving the reforming section 2 exchanges heat with the raw material gas in the heat exchanger 4, and after being cooled to about 170 to 250 ° C., a shift reaction represented by Chemical Formula 2 is caused in the CO shift section 5. .

【００５３】このＣＯシフト後で、ＣＯ濃度は温度に応
じて１％以下まで低減される。ＰＥＦＣ型の燃料電池７
においては、電極のＣＯ被毒が発生するために、ＰＥＦ
Ｃに導入される燃料ガス中のＣＯ濃度は、１０ｐｐｍ以
下に下げる必要がある。そこで、シフト反応後にルテニ
ウム触媒で構成さた前記ＣＯ選択酸化部６を設け、酸化
剤として空気を用いて改質ガスの化２によって示される
酸化反応によりＣＯを１０ｐｐｍ以下まで低減する。After this CO shift, the CO concentration is reduced to less than 1% depending on the temperature. PEFC fuel cell 7
In the case, the electrode poisoning of CO
The CO concentration in the fuel gas introduced into C needs to be reduced to 10 ppm or less. Therefore, after the shift reaction, the CO selective oxidizing section 6 composed of a ruthenium catalyst is provided, and CO is reduced to 10 ppm or less by the oxidation reaction represented by Chemical Modification 2 using air as an oxidizing agent.

【００５４】このときの酸化空気量を前記ＣＯシフト部
５の温度Ｔｃ２と改質ガス流量から判断し、コントロー
ルする。コントロールにおいては、実験と計算から求め
たマップ（空気流量＝関数（Ｔｃ２、改質原料流量））
を使用した。以下に、起動、定常、負荷変動時における
運転方法の詳細を説明する。At this time, the oxidizing air amount is determined and controlled based on the temperature Tc2 of the CO shift section 5 and the reformed gas flow rate. In the control, a map obtained from experiments and calculations (air flow rate = function (Tc2, reforming raw material flow rate))
It was used. Hereinafter, details of the operation method at the time of starting, steady state, and load fluctuation will be described.

【００５５】起動時における運転手順は、図１１に示さ
れるフローチャートに従い行われる。すなわち図９に示
される運転シーケンスに従って改質部を起動した場合の
結果が図３に示される。The operation procedure at the time of startup is performed according to the flowchart shown in FIG. That is, FIG. 3 shows the result when the reforming unit is started in accordance with the operation sequence shown in FIG.

【００５６】前記バーナ１の着火後前記蒸発部３の温度
が所定の温度に達したら水供給を開始し、前記改質器２
内全体に水蒸気を行き渡らせる。その後改質原料を投入
し改質が開始される。前記改質部２の温度が所定の温度
に達したら、前記改質部２は起動完了とみなす。When the temperature of the evaporator 3 reaches a predetermined temperature after the burner 1 is ignited, water supply is started and the reformer 2
Spread water vapor throughout the inside. After that, the reforming raw material is charged and the reforming is started. When the temperature of the reforming section 2 reaches a predetermined temperature, it is considered that the reforming section 2 has been started.

【００５７】前記ＣＯシフト部５については、触媒が活
性温度に達した段階で起動完了とみなす。活性温度に至
らしめる時間を短縮するためにヒータを用いても良い。
前記ＣＯ選択酸化部６については改質開始後、改質ガス
が流れはじめた後に温度上昇を始める。The start of the CO shift unit 5 is considered to be completed when the catalyst reaches the activation temperature. A heater may be used to shorten the time required to reach the activation temperature.
After the start of reforming, the temperature of the CO selective oxidizing section 6 starts to rise after the reformed gas starts flowing.

【００５８】ＣＯ除去のための空気の投入量は、起動用
にあらかじめ用意されたマップに従って、前記ＣＯ選択
酸化部６の温度から投入量が決定される。このマップは
改質原料流量と前記ＣＯ選択酸化部６の温度から決定さ
れ、前記ＣＯシフト部５の温度Ｔｃ２は参照しない。The input amount of air for removing CO is determined from the temperature of the CO selective oxidizing unit 6 according to a map prepared in advance for starting. This map is determined from the flow rate of the reforming raw material and the temperature of the CO selective oxidizing section 6, and does not refer to the temperature Tc2 of the CO shift section 5.

【００５９】前記ＣＯ選択酸化部６の触媒温度が活性下
限に達したのち、一定時間保持した後で触媒温度が適切
な範囲内であれば、前記ＣＯ選択酸化部６は起動完了と
みなされる。前記改質部２、前記ＣＯシフト部５、前記
ＣＯ選択酸化部６が揃って起動完了条件を満たした段階
で改質器は起動完了し、燃料電池スタックに水素を供給
可能となる。After the catalyst temperature of the CO selective oxidizing unit 6 has reached the lower limit of activity, if the catalyst temperature is within an appropriate range after holding for a certain period of time, the CO selective oxidizing unit 6 is considered to be completely started. When the reforming section 2, the CO shift section 5, and the CO selective oxidizing section 6 have all met the startup completion condition, the startup of the reformer is completed, and hydrogen can be supplied to the fuel cell stack.

【００６０】起動停止が頻繁に行われ、前記改質部２が
暖まった状態で起動された場合、前記ＣＯ選択酸化部６
の温度指示が最初から高い場合がある。しかし、停止中
で自然放熱中の選択酸化部６の温度分布はばらつきがあ
り、温度が低い部分もある。この場合、酸化空気を投入
直後は温度が高い値を指示していても、温度の低い部分
で水分の凝縮が発生し、しばらくすると触媒全体の温度
が低下することがある。一定時間保持した後に活性判断
を行うことで、上記の事態による不具合を回避できる。When the reforming section 2 is started in a warm state because the starting and stopping are performed frequently, the CO selective oxidizing section 6
Temperature indication may be high from the beginning. However, the temperature distribution of the selective oxidation section 6 during stoppage and during natural heat radiation varies, and there is a portion where the temperature is low. In this case, even if the temperature indicates a high value immediately after the oxidizing air is supplied, water condensation occurs in a low temperature portion, and after a while, the temperature of the entire catalyst may decrease. By performing the activity determination after holding for a certain period of time, it is possible to avoid the problem caused by the above situation.

【００６１】また、選択酸化空気流量のマップとして、
本実施例においては下記の２種のマップを用いた。Ｔ３
１１は選択酸化触媒の活性下限温度を、Ｔａは選択酸化
エア投入開始温度を意味している。表２に示されるマッ
プ２を用いて、起動を行った結果が図１０（Ａ）に示さ
れる。マップ２ではＴｃ３がＴａに達したら、ある程度
多めの流量を投入する。触媒温度が活性下限になった
ら、流量を減らして起動時として設定した流量に変更す
る。As a map of the flow rate of the selected oxidizing air,
In the present embodiment, the following two maps are used. T3
Numeral 11 denotes the lower limit temperature of the activity of the selective oxidation catalyst, and Ta denotes the temperature at which selective oxidation air is introduced. FIG. 10A shows the result of starting using Map 2 shown in Table 2. In Map 2, when Tc3 reaches Ta, a somewhat larger flow rate is input. When the catalyst temperature reaches the lower limit of the activity, the flow rate is reduced and changed to the flow rate set at the start.

【表２】 [Table 2]

【００６２】一方で表１に示されるマップ１では起動完
了時に最終的に投入する流量にいたるまで、４分割して
細かに流量を制御していく。マップ１を用いた結果が図
１０（Ｂ）に示される。上述したマップ２とＣＯが低減
されるまでの起動時間に大きな違いは無いものの、冬季
など、選択酸化部で水凝縮が起き易い環境においては、
図中にも観測されるように、酸化エアを投入した直後に
水素が燃焼して生成される水が凝縮し、選択酸化部の温
度が下がっていることが分かる。このような場合、一度
に多量の酸化剤を吹き込まないマップ１の方が優れた結
果を得ることが可能である。On the other hand, in Map 1 shown in Table 1, the flow rate is finely controlled by dividing into four parts until the flow rate is finally input at the completion of the startup. The result using the map 1 is shown in FIG. Although there is no significant difference between the above-described map 2 and the startup time until the CO is reduced, in an environment where water condensation easily occurs in the selective oxidation unit, such as in winter,
As can be seen from the figure, it can be seen that the water produced by the combustion of hydrogen condenses immediately after the oxidizing air is introduced, and the temperature of the selective oxidizing section has dropped. In such a case, the map 1 in which a large amount of the oxidizing agent is not blown at once can obtain better results.

【表１】 [Table 1]

【００６３】一方で、マップ１のデータを変更すること
でマップ２の制御に以降することは簡単であるから、シ
ステムとしてはマップ１に伴う制御方法を採用し、必要
に応じてマップ２に準じたデータ内容のマップを呼び出
して制御を行えば、大きな変更なしで両者の制御を行う
ことが出来る。On the other hand, since it is easy to change the data of the map 1 to control the map 2 and thereafter, the system adopts the control method associated with the map 1 and, if necessary, complies with the map 2. If the control is performed by calling up the map of the data contents, both can be controlled without major changes.

【００６４】定常時における運転手順は、図１２に示さ
れるフローチャートに従い行われる。酸化エア流量と前
記バーナ１において燃焼させる改質原料となる天然ガス
１３Ａの量は常にコントロールされる。The operating procedure in the steady state is performed according to the flowchart shown in FIG. The flow rate of the oxidizing air and the amount of the natural gas 13A serving as the reforming material burned in the burner 1 are constantly controlled.

【００６５】前記改質部２の温度Ｔｃ１と、前記ＣＯシ
フト部５の温度Ｔｃ２と前記ＣＯ選択酸化部６の温度Ｔ
ｃ３と、前記改質部２の壁面温度Ｔｃｗの何れかが許容
温度範囲外になった場合はただちに発電を中止する。The temperature Tc1 of the reforming section 2, the temperature Tc2 of the CO shift section 5, and the temperature Tc of the CO selective oxidizing section 6
If either c3 or the wall surface temperature Tcw of the reforming section 2 falls outside the allowable temperature range, power generation is immediately stopped.

【００６６】前記ＣＯ選択酸化部６には改質原料流量
と、前記ＣＯシフト部５の温度Ｔｃ２のマップデータか
ら決まる流量の酸化剤が供給される。The oxidizing agent is supplied to the CO selective oxidizing section 6 at a flow rate determined from the reforming raw material flow rate and the map data of the temperature Tc2 of the CO shift section 5.

【００６７】負荷の増加時における運転手順は、図１３
に示される負荷の増加時のフローチャートに従い行われ
る。酸化エア流量と前記バーナ１で燃焼させる改質原料
となる天然ガス１３Ａ量は常にコントロールされる。The operating procedure when the load increases is shown in FIG.
Is performed according to the flowchart at the time of increasing the load shown in FIG. The flow rate of the oxidizing air and the amount of the natural gas 13A serving as the reforming raw material burned by the burner 1 are constantly controlled.

【００６８】前記改質部２の温度Ｔｃ１と、前記ＣＯシ
フト部５の温度Ｔｃ２と前記ＣＯ選択酸化部６の温度Ｔ
ｃ３と、前記改質部２の壁面温度Ｔｃｗの何れかが許容
温度範囲外になった場合はただちに発電を中止する。The temperature Tc1 of the reforming section 2, the temperature Tc2 of the CO shift section 5, and the temperature Tc of the CO selective oxidizing section 6.
If either c3 or the wall surface temperature Tcw of the reforming section 2 falls outside the allowable temperature range, power generation is immediately stopped.

【００６９】水供給量（水蒸気量）を所定の流量に増加
させた後３分後に、前記ＣＯ選択酸化部６への酸化剤流
量を増加させ、ただちに改質原料流量を増加させる。Three minutes after the water supply amount (water vapor amount) is increased to a predetermined flow rate, the flow rate of the oxidizing agent to the CO selective oxidation section 6 is increased, and the flow rate of the reforming raw material is immediately increased.

【００７０】負荷の減少時における運転手順は、図１４
に示される負荷の減少時のフローチャートに従い行われ
る。酸化エア流量と前記バーナ１で燃焼させる改質原料
となる天然ガス１３Ａ量は常にコントロールされる。The operation procedure when the load decreases is shown in FIG.
Is performed according to the flowchart at the time of load reduction shown in FIG. The flow rate of the oxidizing air and the amount of the natural gas 13A serving as the reforming raw material burned by the burner 1 are constantly controlled.

【００７１】前記改質部２の温度Ｔｃ１と、前記ＣＯシ
フト部５の温度Ｔｃ２と前記ＣＯ選択酸化部６の温度Ｔ
ｃ３と、前記改質部２の壁面温度Ｔｃｗの何れかが許容
温度範囲外になった場合はただちに発電を中止する。The temperature Tc1 of the reforming section 2, the temperature Tc2 of the CO shift section 5, and the temperature Tc of the CO selective oxidizing section 6
If either c3 or the wall surface temperature Tcw of the reforming section 2 falls outside the allowable temperature range, power generation is immediately stopped.

【００７２】改質原料を減少させた後、ただちに水供給
量（水蒸気量）と前記ＣＯ選択酸化部６に供給される酸
化剤の空気流量を減少させる。Immediately after reducing the amount of the reforming raw material, the water supply amount (steam amount) and the air flow rate of the oxidizing agent supplied to the CO selective oxidizing section 6 are reduced.

【００７３】なお負荷減少時は、水蒸気と改質原料を同
時に減らしても、負荷減少時のＣＯ濃度変化が示される
図１５から明らかなようにＣＯの増加は生じなかった。When the load was reduced, even if the amount of steam and the amount of the reforming material were reduced at the same time, the increase in CO did not occur as is apparent from FIG.

【００７４】上述の実施形態および実施例は、説明のた
めに例示したもので、本発明としてはそれらに限定され
るものでは無く、特許請求の範囲、発明の詳細な説明お
よび図面の記載から当業者が認識することができる本発
明の技術的思想に反しない限り、変更および付加が可能
である。The above-described embodiments and examples have been described by way of example, and the present invention is not limited thereto. The present invention is not limited to the claims, the detailed description of the invention, and the drawings. Modifications and additions are possible without departing from the technical idea of the present invention that can be recognized by those skilled in the art.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明の実施形態および実施例の天然ガス燃料
電池システムを示すブロック図である。FIG. 1 is a block diagram showing a natural gas fuel cell system according to embodiments and examples of the present invention.

【図２】本実施形態におけるシフト温度およびＣＯ濃度
の平衡濃度を示す線図である。FIG. 2 is a diagram showing an equilibrium concentration of a shift temperature and a CO concentration in the present embodiment.

【図３】本実施形態における平衡計算値と実験データと
の関係を示す線図である。FIG. 3 is a diagram showing a relationship between an equilibrium calculation value and experimental data in the present embodiment.

【図４】本実施形態における負荷増加時のＣＯ濃度を示
す線図である。FIG. 4 is a diagram showing the CO concentration when the load is increased in the embodiment.

【図５】本実施形態における水蒸気量き影響による平衡
濃度を示す線図である。FIG. 5 is a diagram showing an equilibrium concentration due to the influence of the amount of water vapor in the present embodiment.

【図６】本実施形態におけるタイムラグ１．５分の場合
のＣＯ濃度の変化を示す線図である。FIG. 6 is a diagram showing a change in CO concentration when a time lag is 1.5 minutes in the present embodiment.

【図７】本実施形態におけるタイムラグ３分の場合のＣ
Ｏ濃度の変化を示す線図である。FIG. 7 is a diagram illustrating a time lag of 3 minutes according to the embodiment;
FIG. 4 is a diagram illustrating a change in O concentration.

【図８】本実施形態におけるタイムラグ５分の場合のＣ
Ｏ濃度の変化を示す線図である。FIG. 8 is a time lag of 5 minutes according to the embodiment;
FIG. 4 is a diagram illustrating a change in O concentration.

【図９】本実施例における改質器運転シーケンスの手順
を示すチャート図である。FIG. 9 is a chart showing a procedure of a reformer operation sequence in this embodiment.

【図１０】本実施例におけるマップ１および２に従い起
動した場合のＣＯ濃度の変化をそれぞれ示す線図であ
る。FIG. 10 is a diagram showing a change in CO concentration when activated according to maps 1 and 2 in the embodiment.

【図１１】本実施例における起動時の運転手順を示すチ
ャート図である。FIG. 11 is a chart showing an operation procedure at the time of startup in the present embodiment.

【図１２】本実施例における定常運転時の運転手順を示
すチャート図である。FIG. 12 is a chart showing an operation procedure at the time of steady operation in the present embodiment.

【図１３】本実施例における負荷増加時の運転手順を示
すチャート図である。FIG. 13 is a chart showing an operation procedure when a load is increased in the embodiment.

【図１４】本実施例における負荷減少時の運転手順を示
すチャート図である。FIG. 14 is a chart showing an operation procedure when the load is reduced in the embodiment.

【図１５】本実施例における負荷減少時の水蒸気および
改質原料を減少させた時のＣＯ濃度の変化を示す線図で
ある。FIG. 15 is a graph showing changes in CO concentration when the amount of steam and the amount of reforming raw material are reduced when the load is reduced in the embodiment.

【符号の説明】[Explanation of symbols]

２ 改質部 ５ ＣＯシフト部 ６ ＣＯ選択酸化部 2 Reforming unit 5 CO shift unit 6 CO selective oxidation unit

フロントページの続き Ｆターム(参考） 4G040 EA03 EA06 EB32 EB43 EB46 4G140 EA03 EA06 EB32 EB43 EB46 5H026 AA06 EE12 HH00 HH05 HH06 HH08 5H027 AA02 BA01 BA09 BA17 KK42 KK48 KK52 MM12 MM14 Continued on front page F term (reference) 4G040 EA03 EA06 EB32 EB43 EB46 4G140 EA03 EA06 EB32 EB43 EB46 5H026 AA06 EE12 HH00 HH05 HH06 HH08 5H027 AA02 BA01 BA09 BA17 KK42 KK48 KK52 MM12 MM14

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 燃料電池用の水蒸気改質器を備えた燃料
電池用改質装置において、 改質部の出口温度とシフト部の触媒温度とＣＯ選択酸化
部の触媒温度に基づき改質組成を推定することにより、
起動時における運転を制御するようにしたことを特徴と
する燃料電池用改質装置の運転制御方法。In a fuel cell reforming apparatus provided with a fuel cell steam reformer, a reforming composition is determined based on an outlet temperature of a reforming section, a catalyst temperature of a shift section, and a catalyst temperature of a CO selective oxidizing section. By estimating,
An operation control method for a reformer for a fuel cell, wherein operation at the time of startup is controlled. 【請求項２】 請求項１において、 前記ＣＯ選択酸化部の触媒温度に従って該ＣＯ選択酸化
部に供給するＣＯ酸化剤の量を制御することにより、起
動時における運転を制御するようにしたことを特徴とす
る燃料電池用改質装置の運転制御方法。2. The method according to claim 1, wherein the amount of the CO oxidizing agent supplied to the CO selective oxidizing unit is controlled according to the catalyst temperature of the CO selective oxidizing unit, thereby controlling the operation at the time of startup. A method for controlling the operation of a reformer for a fuel cell. 【請求項３】 請求項２において、 前記改質部の出口温度を一定範囲内に保持するととも
に、前記シフト部の触媒温度に従って前記ＣＯ選択酸化
部に供給するＣＯ酸化剤の量を制御することにより、定
常時における運転を制御するようにしたことを特徴とす
る燃料電池用改質装置の運転制御方法。3. The CO-oxidizing agent according to claim 2, wherein an outlet temperature of the reforming section is maintained within a certain range, and an amount of a CO oxidant supplied to the CO selective oxidizing section is controlled according to a catalyst temperature of the shift section. The operation control method for a fuel cell reforming apparatus according to claim 1, wherein the operation in a steady state is controlled. 【請求項４】 請求項３において、 負荷変動時に前記改質部の出口温度を一定範囲内に保持
するように運転を制御するようにしたことを特徴とする
燃料電池用改質装置の運転制御方法。4. The operation control of a reformer for a fuel cell according to claim 3, wherein the operation is controlled so that the outlet temperature of the reformer is maintained within a certain range when the load fluctuates. Method. 【請求項５】 請求項４において、 負荷が増加する場合は、水または水蒸気の供給量および
前記ＣＯ選択酸化部に供給するＣＯ酸化剤の量を先行し
て増加することにより、負荷変動時における運転を制御
するようにしたことを特徴とする燃料電池用改質装置の
運転制御方法。5. The load according to claim 4, wherein when the load increases, the supply amount of water or steam and the amount of the CO oxidant supplied to the CO selective oxidizing unit are increased in advance, so that the load at the time of load change is increased. An operation control method for a fuel cell reformer, wherein operation is controlled. 【請求項６】 請求項５において、 負荷が減少する場合は、改質原料流量を先行して減少す
ることにより、負荷変動時における運転を制御するよう
にしたことを特徴とする燃料電池用改質装置の運転制御
方法。6. The fuel cell reformer according to claim 5, wherein when the load decreases, the reforming raw material flow rate is reduced in advance to control the operation when the load changes. Operation control method for quality equipment.
JP2001050704A 2001-02-26 2001-02-26 Operation control method for reformer for fuel cell Expired - Fee Related JP4110354B2 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004116934A (en) * 2002-09-27 2004-04-15 Aisin Seiki Co Ltd Method of igniting reforming unit burner for fuel cell, and fuel cell system using the same
WO2005000737A1 (en) * 2003-06-27 2005-01-06 Ebara Ballard Corporation Fuel reformer
JP2006347788A (en) * 2005-06-14 2006-12-28 T Rad Co Ltd Method for controlling load of reforming system
JP2008105900A (en) * 2006-10-25 2008-05-08 Aisin Seiki Co Ltd Reforming apparatus

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004116934A (en) * 2002-09-27 2004-04-15 Aisin Seiki Co Ltd Method of igniting reforming unit burner for fuel cell, and fuel cell system using the same
WO2005000737A1 (en) * 2003-06-27 2005-01-06 Ebara Ballard Corporation Fuel reformer
US7635399B2 (en) 2003-06-27 2009-12-22 Ebara Corporation Fuel reformer
JP2006347788A (en) * 2005-06-14 2006-12-28 T Rad Co Ltd Method for controlling load of reforming system
JP2008105900A (en) * 2006-10-25 2008-05-08 Aisin Seiki Co Ltd Reforming apparatus

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