JP5461880B2 - Fuel cell reformer - Google Patents

Fuel cell reformer Download PDF

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JP5461880B2
JP5461880B2 JP2009110057A JP2009110057A JP5461880B2 JP 5461880 B2 JP5461880 B2 JP 5461880B2 JP 2009110057 A JP2009110057 A JP 2009110057A JP 2009110057 A JP2009110057 A JP 2009110057A JP 5461880 B2 JP5461880 B2 JP 5461880B2
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reforming
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vaporization
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昭 藤生
正天 門脇
琢也 梶田
嘉孝 原
佳展 西村
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Eneos Corp
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JXTG Nippon Oil and Energy Corp
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Description

本発明は、原燃料を改質して燃料電池で使用される改質ガスを生成する燃料電池用改質装置に関する。   The present invention relates to a reformer for a fuel cell that reforms raw fuel to generate a reformed gas used in a fuel cell.

近年、エネルギー変換効率が高く、かつ、発電反応により有害物質を発生しない燃料電池が注目を浴びている。こうした燃料電池の一つとして、固体高分子形燃料電池が知られている。   In recent years, fuel cells that have high energy conversion efficiency and do not generate harmful substances due to power generation reactions have attracted attention. As one of such fuel cells, a polymer electrolyte fuel cell is known.

固体高分子形燃料電池は、電解質膜である固体高分子膜を燃料極と空気極との間に配した基本構造を有し、燃料極に水素を含む燃料ガス、空気極に酸素を含む酸化剤ガスを供給し、以下の電気化学反応により発電する装置である。   A polymer electrolyte fuel cell has a basic structure in which a polymer electrolyte membrane, which is an electrolyte membrane, is disposed between a fuel electrode and an air electrode. The fuel electrode contains hydrogen and the air electrode contains oxygen. It is a device that supplies the agent gas and generates power by the following electrochemical reaction.

燃料極：Ｈ２→２Ｈ＋+２ｅ−・・・・（１）
空気極：１／２Ｏ２+２Ｈ＋+２ｅ−→Ｈ２Ｏ・・・・（２）
実用的には、固体高分子形燃料電池の燃料となる水素は、比較的容易かつ安価に入手可能な天然ガス、ナフサ等の炭化水素系ガスまたはメタノール等のアルコール類の原燃料ガスと水蒸気とを混合して、改質部で改質することで得る手法が採用されている。改質により得られた水素ガスは燃料電池の燃料極に供給され、発電に用いられる。 The fuel electrode: H 2 → 2H + + 2e - ···· (1)
Cathode: 1 / 2O 2 + 2H + + 2e - → H 2 O ···· (2)
Practically, hydrogen used as a fuel for a polymer electrolyte fuel cell is a natural gas, a hydrocarbon gas such as naphtha, or a raw fuel gas of alcohols such as methanol and water vapor, which can be obtained relatively easily and inexpensively. The technique obtained by mixing and reforming in the reforming section is employed. Hydrogen gas obtained by reforming is supplied to the fuel electrode of the fuel cell and used for power generation.

図１は、従来の燃料電池システムの構成を示す概略図である。従来、燃料電池システム３００では、まず、原燃料（天然ガスやＬＰＧなどの炭化水素系ガス）が脱硫部３１０に供給され、原燃料から硫黄成分が除去される。   FIG. 1 is a schematic diagram showing the configuration of a conventional fuel cell system. Conventionally, in the fuel cell system 300, first, raw fuel (hydrocarbon gas such as natural gas or LPG) is supplied to the desulfurization unit 310, and sulfur components are removed from the raw fuel.

硫黄成分が除去された原燃料は改質部３２０に供給される。改質部３２０は、バーナー３２２で熱した触媒に原燃料を通すことにより原燃料を水蒸気改質し、改質ガスを生成する。   The raw fuel from which the sulfur component has been removed is supplied to the reforming unit 320. The reforming unit 320 steam-reforms the raw fuel by passing the raw fuel through the catalyst heated by the burner 322 to generate a reformed gas.

改質部３２０の起動時には、改質部３２０を昇温するために、バーナー３２２に原燃料の一部が供給される。燃料電池４００が安定的に運転できるようになると、バーナー３２２への原燃料の供給を停止し、燃料電池４００から排出される電池オフガスをバーナー３２２に供給することにより、改質部３２０の昇温が図られる。バーナー３２２の燃焼により生じる排ガスは、気化部３３０において改質水と熱交換した後、燃料電池システム３００から外部へ排出される。また、バーナー３２２には、空気が供給され、バーナー３２２の燃焼に用いられる。   When starting up the reforming unit 320, a part of the raw fuel is supplied to the burner 322 in order to raise the temperature of the reforming unit 320. When the fuel cell 400 can be stably operated, the supply of the raw fuel to the burner 322 is stopped, and the battery off gas discharged from the fuel cell 400 is supplied to the burner 322, whereby the temperature of the reforming unit 320 is increased. Is planned. Exhaust gas generated by the combustion of the burner 322 is exhausted from the fuel cell system 300 to the outside after exchanging heat with the reforming water in the vaporization section 330. In addition, air is supplied to the burner 322 and used for combustion of the burner 322.

改質部３２０によって生成された改質ガスは、熱交換部３４０で原燃料に加えられる前の改質水（水蒸気）と熱交換した後、ＣＯ変成部３５０に供給される。ＣＯ変成部３５０では、シフト反応により一酸化炭素が水素に変成される。これにより、水素濃度が高められるとともに、ＣＯ濃度が低減される。   The reformed gas generated by the reforming unit 320 exchanges heat with reformed water (steam) before being added to the raw fuel in the heat exchanging unit 340 and then supplied to the CO converting unit 350. In the CO conversion unit 350, carbon monoxide is converted to hydrogen by a shift reaction. Thereby, the hydrogen concentration is increased and the CO concentration is reduced.

ＣＯ変成部３５０によりＣＯ濃度が低減された改質ガスは、熱交換部３４２で気化部３３０で気化された水蒸気と熱交換した後、ＣＯ除去部３６０に供給される。ＣＯ除去部３６０では、ＣＯ選択酸化触媒を用いたＣＯ酸化反応によりＣＯ濃度がさらに低減される。なお、ＣＯ変成部３５０によりＣＯ濃度が低減された改質ガスには、ＣＯ酸化反応に必要な空気が供給される。   The reformed gas whose CO concentration has been reduced by the CO conversion unit 350 is heat-exchanged with the water vapor evaporated by the vaporization unit 330 by the heat exchange unit 342 and then supplied to the CO removal unit 360. In the CO removal unit 360, the CO concentration is further reduced by the CO oxidation reaction using the CO selective oxidation catalyst. Note that air necessary for the CO oxidation reaction is supplied to the reformed gas whose CO concentration has been reduced by the CO conversion unit 350.

ＣＯ除去部３６０によりＣＯ濃度がさらに低減された改質ガスは、熱交換部３４４で水蒸気と熱交換した後、燃料電池４００の燃料極に供給される。燃料電池４００の空気極には酸化剤として空気が供給され、水素と酸素による電気化学反応により発電が行われる。   The reformed gas whose CO concentration is further reduced by the CO removing unit 360 is heat-exchanged with water vapor by the heat exchanging unit 344 and then supplied to the fuel electrode of the fuel cell 400. Air is supplied as an oxidant to the air electrode of the fuel cell 400, and power is generated by an electrochemical reaction between hydrogen and oxygen.

改質部３２０における改質反応に必要な水蒸気は、燃料電池システム３００の外部から供給された改質水から生成される。具体的には、外部から供給された液体の改質水は、気化部３３０において、バーナー３２２からの排ガスと熱交換することにより気化し、水蒸気となる。気化部３３０により生成した水蒸気は、熱交換部３４２、ＣＯ除去部３６０、熱交換部３４４の順で改質ガスと熱交換した後、ＣＯ変成部３５０、熱交換部３４０の順で改質ガスとさらに熱交換したのち、脱硫された原燃料に混合される。   The water vapor necessary for the reforming reaction in the reforming unit 320 is generated from the reformed water supplied from the outside of the fuel cell system 300. Specifically, the liquid reforming water supplied from the outside is vaporized by exchanging heat with the exhaust gas from the burner 322 in the vaporizing section 330 to become water vapor. The steam generated by the vaporization unit 330 is heat-exchanged with the reformed gas in the order of the heat exchange unit 342, the CO removal unit 360, and the heat exchange unit 344, and then the reformed gas in the order of the CO conversion unit 350 and the heat exchange unit 340. After further heat exchange, it is mixed with the desulfurized raw fuel.

特開２００７−３２６７２４JP2007-326724

従来の燃料電池システムでは、空気比や原燃料の量の変動に起因してバーナーからの排ガスの熱量が変化すると、気化部における改質水の気化ポイントが変動する。これにより、水蒸気の圧力変動や流量変動等が生じるため、改質部における改質反応の制御が困難となる。また、気化部で気化された水蒸気が改質部に導かれる間に、水蒸気の乾き度が変化しやすいため、水蒸気の圧力変動が生じやすくなる要因となっていた。   In the conventional fuel cell system, when the calorific value of the exhaust gas from the burner changes due to fluctuations in the air ratio or the amount of raw fuel, the vaporization point of the reformed water in the vaporization section varies. As a result, fluctuations in the pressure or flow rate of the water vapor occur, making it difficult to control the reforming reaction in the reforming section. In addition, while the steam vaporized in the vaporization section is guided to the reforming section, the dryness of the steam is likely to change.

本発明はこうした課題に鑑みてなされたものであり、その目的は、原燃料の改質に用いられる水蒸気の圧力変動を抑制し、ロバスト性を向上させ、改質部における改質反応の安定性の向上を図ることができる技術の提供にある。   The present invention has been made in view of these problems, and its purpose is to suppress fluctuations in the pressure of water vapor used for reforming raw fuel, improve robustness, and stability of the reforming reaction in the reforming section. It is in the provision of the technology which can aim at improvement.

本発明のある態様は、燃料電池用改質装置である。当該燃料電池用改質装置は、原燃料を水蒸気改質により改質する改質部と、改質部で生成した改質ガスのＣＯ濃度を低減するＣＯ低減部と、改質部の加熱に用いられる燃焼手段から排出される排ガスの熱を用いて、改質部で生成した改質ガスと気化前の改質水との間で熱交換させることにより、前記改質水を加熱する気化前熱交換部と、気化前熱交換部を経由した改質水を気化させる気化部と、を備え、気化部で生じた水蒸気が原燃料とともに改質部に供給されることを特徴とする。   One embodiment of the present invention is a reformer for a fuel cell. The fuel cell reformer includes a reforming unit that reforms raw fuel by steam reforming, a CO reduction unit that reduces the CO concentration of reformed gas generated in the reforming unit, and heating of the reforming unit. Before the vaporization of heating the reformed water by heat exchange between the reformed gas generated in the reforming unit and the reformed water before vaporization using the heat of the exhaust gas discharged from the combustion means used A heat exchange part and a vaporization part for vaporizing the reformed water that has passed through the pre-vaporization heat exchange part are provided, and water vapor generated in the vaporization part is supplied to the reforming part together with the raw fuel.

この態様によれば、気化前熱交換部において改質ガスと熱交換することにより予め昇温された改質水が気化部に供給される。この結果、改質触媒を加熱するための燃焼手段からの排ガスの熱量の変化の影響が低減され、気化部にける気化ポイントが安定し、ロバスト性が向上する。   According to this aspect, the reforming water heated in advance by exchanging heat with the reformed gas in the pre-vaporization heat exchange section is supplied to the vaporization section. As a result, the influence of the change in the amount of heat of the exhaust gas from the combustion means for heating the reforming catalyst is reduced, the vaporization point in the vaporization section is stabilized, and the robustness is improved.

上記態様の燃料電池用改質装置において気化前熱交換部は、ＣＯ低減部に設けられていてもよい。また、ＣＯ低減部は、シフト反応により改質ガスのＣＯ濃度を低減するＣＯ変成部であってもよい。また、気化部に供給される改質水の圧力を減圧する減圧部をさらに備えてもよい。   In the fuel cell reforming apparatus of the above aspect, the pre-vaporization heat exchange section may be provided in the CO reduction section. The CO reduction unit may be a CO conversion unit that reduces the CO concentration of the reformed gas by a shift reaction. Moreover, you may further provide the pressure reduction part which pressure-reduces the pressure of the reforming water supplied to a vaporization part.

本発明によれば、原燃料の改質に用いられる水蒸気の圧力変動を抑制し、ロバスト性を向上させることができる。   ADVANTAGE OF THE INVENTION According to this invention, the pressure fluctuation of the water vapor | steam used for the reforming | reformation of raw fuel can be suppressed, and robustness can be improved.

従来の燃料電池システムの構成を示す概略図である。It is the schematic which shows the structure of the conventional fuel cell system. 実施の形態に係る燃料電池用改質装置を含む燃料電池システムの構成を示す概略図である。It is the schematic which shows the structure of the fuel cell system containing the reformer for fuel cells which concerns on embodiment. 燃料電池用改質装置のより詳細な構成を示す図である。It is a figure which shows the more detailed structure of the reformer for fuel cells.

以下、本発明の実施の形態を図面を参照して説明する。なお、すべての図面において、同様な構成要素には同様の符号を付し、適宜説明を省略する。   Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

図２は、実施の形態に係る燃料電池用改質装置１０を含む燃料電池システム１００の構成を示す概略図である。   FIG. 2 is a schematic diagram showing a configuration of a fuel cell system 100 including the fuel cell reforming apparatus 10 according to the embodiment.

燃料電池用改質装置１０は、脱硫部２０、改質部３０、バーナー３２、ＣＯ変成部６０、熱交換部５０、５２、ＣＯ除去部７０および気化部４０を含む。   The fuel cell reforming apparatus 10 includes a desulfurization unit 20, a reforming unit 30, a burner 32, a CO conversion unit 60, heat exchange units 50 and 52, a CO removal unit 70, and a vaporization unit 40.

まず、原燃料（天然ガスやＬＰＧなどの炭化水素系ガス）が脱硫部２０に供給され、原燃料から硫黄成分が除去される。これにより、硫黄成分が改質部３０や燃料電池１２に含まれる触媒に対して触媒毒として作用し、硫黄被毒により燃料電池用改質装置１０の改質性能や燃料電池１２の発電性能が低下することが抑制される。脱硫部２０は、たとえば、触媒の存在化で硫黄成分を含む原燃料と水素とを反応させて硫黄成分を除去する、いわゆる水素化脱硫方式、またはゼオライト等の硫黄成分を吸着させる吸着方式により原燃料の脱硫を行う。   First, raw fuel (hydrocarbon gas such as natural gas or LPG) is supplied to the desulfurization section 20, and sulfur components are removed from the raw fuel. Thus, the sulfur component acts as a catalyst poison for the catalyst contained in the reforming unit 30 and the fuel cell 12, and the reforming performance of the fuel cell reforming device 10 and the power generation performance of the fuel cell 12 are affected by sulfur poisoning. Decrease is suppressed. For example, the desulfurization unit 20 uses a so-called hydrodesulfurization method in which a raw fuel containing a sulfur component reacts with hydrogen in the presence of a catalyst to remove the sulfur component, or an adsorption method in which a sulfur component such as zeolite is adsorbed. Desulfurize the fuel.

硫黄成分が除去された原燃料は改質部３０に供給される。改質部３０は、たとえば、アルミナ等の担体にルテニウム（Ｒｕ）などの金属触媒が担持された改質触媒からなる触媒層を有する。改質部３０において、バーナー３２で熱した改質触媒下で原燃料が水蒸気改質され、水素（燃料）を約８０％含有する改質ガスが生成する。なお、水蒸気改質時の反応温度は、たとえば約６５０℃〜７００℃の範囲である。   The raw fuel from which the sulfur component has been removed is supplied to the reforming unit 30. For example, the reforming unit 30 has a catalyst layer made of a reforming catalyst in which a metal catalyst such as ruthenium (Ru) is supported on a carrier such as alumina. In the reforming unit 30, the raw fuel is steam reformed under the reforming catalyst heated by the burner 32, and a reformed gas containing about 80% of hydrogen (fuel) is generated. The reaction temperature during steam reforming is, for example, in the range of about 650 ° C to 700 ° C.

改質部３０の起動時には、改質部３０を昇温するために、バーナー３２に原燃料の一部が供給される。燃料電池１２が安定的に運転できるようになると、バーナー３２への原燃料の供給を停止し、燃料電池１２から排出される電池オフガスをバーナー３２に供給することにより、改質部３０の昇温が図られる。バーナー３２の燃焼により生じる排ガスは、気化部４０において改質水と熱交換した後、燃料電池システム１００から外部へ排出される。また、バーナー３２には、空気が供給され、バーナー３２の燃焼に用いられる。   When starting up the reforming unit 30, a part of the raw fuel is supplied to the burner 32 in order to raise the temperature of the reforming unit 30. When the fuel cell 12 can be stably operated, the supply of the raw fuel to the burner 32 is stopped, and the battery off gas discharged from the fuel cell 12 is supplied to the burner 32, whereby the temperature of the reforming unit 30 is increased. Is planned. The exhaust gas generated by the combustion of the burner 32 is discharged from the fuel cell system 100 to the outside after exchanging heat with the reforming water in the vaporization section 40. Further, air is supplied to the burner 32 and used for combustion of the burner 32.

改質部３０によって生成された改質ガスは、熱交換部５０を通過する際に気化部４０を経由した水蒸気と熱交換した後、ＣＯ変成部６０に供給される。ＣＯ変成部６０は、たとえば、酸化銅や酸化亜鉛のペレットからなるＣｕ−Ｚｎ系の触媒からなる触媒層を有し、ＣＯ変成部６０において、シフト反応により一酸化炭素が水素に変成される。これにより、改質ガスの水素濃度が高められるとともに、ＣＯ濃度が０．５％以下に低減される。なお、ＣＯ選択酸化反応は、たとえば、約７０℃〜１８０℃の範囲で行われる。   The reformed gas generated by the reforming unit 30 exchanges heat with water vapor that has passed through the vaporization unit 40 when passing through the heat exchange unit 50, and is then supplied to the CO conversion unit 60. The CO conversion unit 60 includes, for example, a catalyst layer made of a Cu—Zn-based catalyst made of copper oxide or zinc oxide pellets. In the CO conversion unit 60, carbon monoxide is converted to hydrogen by a shift reaction. Thereby, the hydrogen concentration of the reformed gas is increased and the CO concentration is reduced to 0.5% or less. In addition, CO selective oxidation reaction is performed in the range of about 70 to 180 degreeC, for example.

ＣＯ変成部６０によりＣＯ濃度が低減された改質ガスは、熱交換部５２を通過する際に改質水と熱交換した後、ＣＯ除去部７０に供給される。ＣＯ除去部７０は、たとえば、アルミナ等の担体にＲｕを担持したＣＯ選択酸化触媒からなる触媒層を有し、ＣＯ選択酸化触媒を用いたＣＯ酸化反応により改質ガスのＣＯ濃度が１０ｐｐｍ程度にまで低減される。なお、ＣＯ変成部６０によりＣＯ濃度が低減された改質ガスには、ＣＯ酸化反応に必要な空気が供給される。   The reformed gas whose CO concentration has been reduced by the CO converting unit 60 is supplied to the CO removing unit 70 after exchanging heat with the reforming water when passing through the heat exchanging unit 52. The CO removal unit 70 has, for example, a catalyst layer made of a CO selective oxidation catalyst in which Ru is supported on a carrier such as alumina, and the CO concentration of the reformed gas is about 10 ppm by the CO oxidation reaction using the CO selective oxidation catalyst. Reduced to. Note that air necessary for the CO oxidation reaction is supplied to the reformed gas whose CO concentration has been reduced by the CO conversion unit 60.

ＣＯ除去部７０によりＣＯ濃度がさらに低減された改質ガスは、燃料電池１２の燃料極に供給される。燃料電池１２は、たとえば、固体高分子形燃料電池であり、燃料極と空気極との間に固体高分子電解質膜が設けられた膜電極接合体（単セル）が複数積層された積層体を有する。燃料電池１２の空気極には酸化剤として空気が供給され、水素と酸素による電気化学反応により発電が行われる。なお、ＣＯ変成部６０およびＣＯ除去部７０は、改質ガスに含まれるＣＯ濃度の低減に寄与するＣＯ低減部の一例である。   The reformed gas whose CO concentration is further reduced by the CO removing unit 70 is supplied to the fuel electrode of the fuel cell 12. The fuel cell 12 is, for example, a solid polymer fuel cell, and is a laminate in which a plurality of membrane electrode assemblies (single cells) each having a solid polymer electrolyte membrane provided between a fuel electrode and an air electrode are laminated. Have. Air is supplied to the air electrode of the fuel cell 12 as an oxidant, and power is generated by an electrochemical reaction between hydrogen and oxygen. The CO conversion unit 60 and the CO removal unit 70 are examples of a CO reduction unit that contributes to a reduction in the concentration of CO contained in the reformed gas.

改質部３０における改質反応に必要な水蒸気は、燃料電池システム１００の外部から供給された改質水から生成される。改質水は、逆浸透膜とイオン交換樹脂等を備えた水処理装置（図示せず）により上水を処理することにより生成される。水処理装置により上水の導電率が低下するとともに、有機物の混入が抑制される。改質水の供給量は、改質水供給ポンプ９０の出力を調整することで適宜制御される。   The steam necessary for the reforming reaction in the reforming unit 30 is generated from the reformed water supplied from the outside of the fuel cell system 100. The reformed water is generated by treating the clean water with a water treatment device (not shown) provided with a reverse osmosis membrane and an ion exchange resin. The water treatment device reduces the conductivity of clean water and suppresses the mixing of organic substances. The supply amount of the reforming water is appropriately controlled by adjusting the output of the reforming water supply pump 90.

外部から供給された液体の改質水は、熱交換部５２、ＣＯ変成部６０の順で、改質ガスと熱交換することにより昇温した後、気化部４０に供給される。改質水は、ＣＯ変成部６０において改質ガスと熱交換する際に蒸発し始める。さらに、気化部４０において、バーナー３２からの排ガスと熱交換することにより気化が完了する。気化部４０で気化された水蒸気は、原燃料とともに改質部３０に供給される。なお、熱交換部５２およびＣＯ変成部６０における熱交換は、改質水の気化が完了する前に改質ガスと熱交換を行う「気化前熱交換部」の一例である。   The liquid reforming water supplied from outside is heated up by heat exchange with the reformed gas in the order of the heat exchange unit 52 and the CO conversion unit 60, and then supplied to the vaporization unit 40. The reformed water starts to evaporate when heat is exchanged with the reformed gas in the CO shift section 60. Further, vaporization is completed by exchanging heat with the exhaust gas from the burner 32 in the vaporization section 40. The water vapor evaporated in the vaporization unit 40 is supplied to the reforming unit 30 together with the raw fuel. The heat exchange in the heat exchange unit 52 and the CO conversion unit 60 is an example of a “pre-vaporization heat exchange unit” that performs heat exchange with the reformed gas before vaporization of the reformed water is completed.

以上説明した燃料電池用改質装置１０の構成によれば、熱交換部５２およびＣＯ変成部６０において改質ガスと熱交換することにより予め昇温された改質水が気化部４０に供給されるため、バーナー３２からの排ガスの熱量の変化の影響が低減され、気化部４０にける気化ポイントが安定し、ロバスト性が向上する。   According to the configuration of the fuel cell reforming apparatus 10 described above, the reforming water heated in advance by exchanging heat with the reformed gas in the heat exchanging unit 52 and the CO converting unit 60 is supplied to the vaporizing unit 40. Therefore, the influence of the change in the calorific value of the exhaust gas from the burner 32 is reduced, the vaporization point in the vaporization unit 40 is stabilized, and the robustness is improved.

改質水が気化部４０に供給される経路、本実施の形態では、熱交換部５２とＣＯ変成部６０との間に、改質水の圧力を減圧する減圧部８０が設けられている。減圧部８０は、たとえば、オリフィス、キャピラリーである。   In the present embodiment, a decompression unit 80 for reducing the pressure of the reforming water is provided between the heat exchange unit 52 and the CO conversion unit 60 in the path through which the reforming water is supplied to the vaporization unit 40. The decompression unit 80 is, for example, an orifice or a capillary.

減圧部８０により減圧を行うことにより、改質水が蒸発したときの乾き度を上昇させることができる。これにより、バーナー３２からの排ガスの熱量に影響されずに、乾き度の高い（１００％以上）水蒸気を安定的に得ることができ、水蒸気の圧力変動を抑制することができる。また、ＣＯ変成部６０の冷却に乾き度が１００％以下の水蒸気が使用されることにより、水蒸気の温度の変化が抑制され、ＣＯ変成部６０の温度を安定させる効果も生じる。なお、減圧部８０を通過する前の改質水の圧力および温度は、たとえば、それぞれ１５０ｋＰａ、２０℃である。また、減圧部８０を通過し、気化部４０に導入される前の改質水の圧力、温度、乾き度は、たとえば、それぞれ１３０ｋＰａ、１０６℃、９９％である。   By performing decompression by the decompression unit 80, it is possible to increase the degree of dryness when the reforming water evaporates. Thereby, it is possible to stably obtain water vapor having a high dryness (100% or more) without being influenced by the amount of heat of the exhaust gas from the burner 32, and to suppress the pressure fluctuation of the water vapor. In addition, the use of water vapor having a dryness of 100% or less for cooling the CO conversion unit 60 suppresses a change in the temperature of the water vapor, thereby producing an effect of stabilizing the temperature of the CO conversion unit 60. The pressure and temperature of the reforming water before passing through the decompression unit 80 are, for example, 150 kPa and 20 ° C., respectively. Further, the pressure, temperature, and dryness of the reformed water that has passed through the decompression unit 80 and before being introduced into the vaporization unit 40 are, for example, 130 kPa, 106 ° C., and 99%, respectively.

図３は、燃料電池用改質装置１０のより詳細な構成を示す図である。燃料電池用改質装置１０は、改質ユニット２１０、熱交換部５２およびＣＯ除去部７０を含む。   FIG. 3 is a diagram showing a more detailed configuration of the fuel cell reforming apparatus 10. The fuel cell reforming apparatus 10 includes a reforming unit 210, a heat exchanging unit 52, and a CO removing unit 70.

改質ユニット２１０は、多重塔体状に一体化された改質部３０およびＣＯ変成部６０と、バーナー３２とを含む。   The reforming unit 210 includes a reforming unit 30 and a CO conversion unit 60 that are integrated in a multi-column shape, and a burner 32.

バーナー３２は、空気取入口３４から取り入れた空気と燃料取入口３６から取り入れた原燃料（または電池オフガス）とを混合して燃焼させる。バーナー３２で原燃料ガス等が燃焼することによって、１２００〜１３００℃の高温の排ガス（燃焼排ガス）が発生する。   The burner 32 mixes and burns the air taken in from the air intake 34 and the raw fuel (or cell off gas) taken in from the fuel intake 36. When the raw fuel gas or the like is burned in the burner 32, high-temperature exhaust gas (combustion exhaust gas) of 1200 to 1300 ° C. is generated.

バーナー３２の上方に、バーナー３２からの排ガスを上方へ導く円筒状の燃焼筒２２０が設けられている。燃焼筒２２０の外側には、改質部（改質反応塔）３０が設けられている。燃焼筒２２０と改質部３０との間に排ガス流路２２２が形成されている。バーナー３２からの排ガスは、燃焼筒２２０の上方で折り返し、排ガス流路２２２に導かれる。排ガス流路２２２は、改質部３０の下部で上方に折り返し、改質部３０の外側を通り、改質ユニット２１０の上部に設けられた排ガス室２２６に通じている。排ガスは、排ガス室２２６を経由して改質ユニット２１０の外部に排出される。   A cylindrical combustion cylinder 220 is provided above the burner 32 to guide the exhaust gas from the burner 32 upward. A reforming section (reforming reaction tower) 30 is provided outside the combustion cylinder 220. An exhaust gas flow path 222 is formed between the combustion cylinder 220 and the reforming unit 30. The exhaust gas from the burner 32 is turned up above the combustion cylinder 220 and guided to the exhaust gas passage 222. The exhaust gas flow path 222 is folded upward at the lower part of the reforming unit 30, passes through the outside of the reforming unit 30, and communicates with the exhaust gas chamber 226 provided at the upper part of the reforming unit 210. The exhaust gas is discharged outside the reforming unit 210 through the exhaust gas chamber 226.

原燃料と水蒸気が混合された混合ガスは、原燃料供給路２６０を経由して改質ユニット２１０の外部から改質部３０に供給される。   The mixed gas in which the raw fuel and water vapor are mixed is supplied to the reforming unit 30 from the outside of the reforming unit 210 via the raw fuel supply path 260.

改質部３０は、排ガス流路２２２を介して燃焼筒２２０の外側に設けられている。改質部３０は、二重構造になっており、触媒層２３０が設けられた内側流路２３２と、内側流路２３２の外側に設けられた外側流路２３４とを有する。内側流路２３２の下部と、外側流路２３４の下部とが連通されており、内側流路２３２において生成した改質ガスは、外側流路２３４を通って改質ユニット２１０の上部に設けられた改質ガス室２４０に導かれる。   The reforming unit 30 is provided outside the combustion cylinder 220 via the exhaust gas passage 222. The reforming unit 30 has a double structure, and includes an inner channel 232 provided with the catalyst layer 230 and an outer channel 234 provided outside the inner channel 232. The lower part of the inner flow path 232 and the lower part of the outer flow path 234 are communicated, and the reformed gas generated in the inner flow path 232 passes through the outer flow path 234 and is provided in the upper part of the reforming unit 210. It is guided to the reformed gas chamber 240.

改質部３０およびバーナー３２の外側には、断熱部材２５０を介して、ＣＯ変成部６０が設けられている。改質ガス室２４０とＣＯ変成部６０とは配管２４２により接続されており、改質ガス室２４０から改質ガスがＣＯ変成部６０に供給される。   A CO conversion unit 60 is provided outside the reforming unit 30 and the burner 32 via a heat insulating member 250. The reformed gas chamber 240 and the CO conversion unit 60 are connected by a pipe 242, and the reformed gas is supplied from the reformed gas chamber 240 to the CO conversion unit 60.

ＣＯ変成部６０は、二重構造になっており、内側流路６２と、内側流路６２の外側に設けられ、触媒層６４が設けられた外側流路６６とを有する。内側流路６２の下部と、外側流路６６の下部とが連通されており、内側流路６２を通過した改質ガスは、外側流路６６に導かれる。外側流路６６に設けられた触媒層６４によりシフト反応が進行し、改質ガスのＣＯ濃度が低減される。   The CO conversion unit 60 has a double structure, and includes an inner flow path 62 and an outer flow path 66 provided outside the inner flow path 62 and provided with a catalyst layer 64. A lower portion of the inner flow path 62 and a lower portion of the outer flow path 66 are communicated, and the reformed gas that has passed through the inner flow path 62 is guided to the outer flow path 66. The shift reaction proceeds by the catalyst layer 64 provided in the outer flow path 66, and the CO concentration of the reformed gas is reduced.

ＣＯ濃度が低減された改質ガスは、改質ユニット２１０の外部に送られ、熱交換部５２を経由して、ＣＯ除去部７０に供給される。ＣＯ濃度が低減された改質ガスには、ＣＯ変成部６０の下流側において空気取入口６８を経由して空気が加えられる。   The reformed gas having a reduced CO concentration is sent to the outside of the reforming unit 210 and supplied to the CO removing unit 70 via the heat exchange unit 52. Air is added to the reformed gas having a reduced CO concentration via the air intake 68 on the downstream side of the CO shift section 60.

改質水は、熱交換部５２において改質ガスと熱交換することにより昇温された後、減圧部８０により減圧される。減圧部８０により減圧された改質水は、ＣＯ変成部６０の周囲に設けられた螺旋状の配管を通過する際に、ＣＯ変成部６０を通過する改質ガスと熱交換し、蒸発し始める。   The reformed water is heated by exchanging heat with the reformed gas in the heat exchanging section 52 and then depressurized by the decompression section 80. The reformed water decompressed by the decompression unit 80 exchanges heat with the reformed gas passing through the CO transforming unit 60 and starts to evaporate when passing through the spiral pipe provided around the CO transforming unit 60. .

ＣＯ変成部６０において昇温された改質水は、排ガス室２２６に設けられた気化部４０において排ガスと熱交換することにより気化が完了し、乾き度が１００％以上の水蒸気となる。気化部４０で生成した水蒸気は、改質ガス室２４０に設けられた熱交換部５０において改質ガスと熱交換した後、原燃料に加えられ、改質部３０において原燃料の改質に用いられる。   The reformed water whose temperature has been raised in the CO conversion unit 60 is vaporized by exchanging heat with the exhaust gas in the vaporization unit 40 provided in the exhaust gas chamber 226, and becomes a water vapor having a dryness of 100% or more. The water vapor generated in the vaporization section 40 is added to the raw fuel after heat exchange with the reformed gas in the heat exchange section 50 provided in the reformed gas chamber 240, and used for reforming the raw fuel in the reforming section 30. It is done.

本発明は、上述の各実施の形態に限定されるものではなく、当業者の知識に基づいて各種の設計変更等の変形を加えることも可能であり、そのような変形が加えられた実施の形態も本発明の範囲に含まれうるものである。   The present invention is not limited to the above-described embodiments, and various modifications such as design changes can be added based on the knowledge of those skilled in the art. The form can also be included in the scope of the present invention.

例えば、上述の実施の形態では、減圧部８０はＣＯ変成部６０で熱交換する前の改質水の減圧に用いられているが、減圧部８０はＣＯ変成部６０で熱交換した後の改質水が通る経路に設けられていてもよい。   For example, in the above-described embodiment, the decompression unit 80 is used for decompressing the reformed water before heat exchange at the CO conversion unit 60, but the decompression unit 80 is modified after heat exchange at the CO conversion unit 60. You may be provided in the path | route along which quality water passes.

また、気化部４０で気化される前の改質水をＣＯ除去部７０で熱交換させることにより昇温させてもよい。   Alternatively, the temperature of the reformed water before being vaporized by the vaporization unit 40 may be increased by causing the CO removal unit 70 to exchange heat.

１０ 燃料電池用改質装置、１２ 燃料電池、２０ 脱硫部、３０ 改質部、３２ バーナー、３４ 空気取入口、３６ 燃料取入口、４０ 気化部、５０ 熱交換部、５２ 熱交換部、６０ ＣＯ変成部、６２ 内側流路、 ６４ 触媒層、６６ 外側流路、６８ 空気取入口、７０ ＣＯ除去部、８０ 減圧部、１００ 燃料電池システム、２１０ 改質ユニット、２２０ 燃焼筒、２２２ 排ガス流路、２２６ 排ガス室、２３０ 触媒層、２３２ 内側流路、２３４ 外側流路、２４０ 改質ガス室、２５０ 断熱部材、２６０ 原燃料供給路 DESCRIPTION OF SYMBOLS 10 Fuel cell reformer, 12 Fuel cell, 20 Desulfurization section, 30 Reforming section, 32 Burner, 34 Air intake, 36 Fuel intake, 40 Vaporization section, 50 Heat exchange section, 52 Heat exchange section, 60 CO Metamorphic section, 62 inner flow path, 64 catalyst layer, 66 outer flow path, 68 air intake, 70 CO removal section, 80 decompression section, 100 fuel cell system, 210 reforming unit, 220 combustion cylinder, 222 exhaust gas flow path, 226 Exhaust gas chamber, 230 catalyst layer, 232 inner flow path, 234 outer flow path, 240 reformed gas chamber, 250 heat insulating member, 260 raw fuel supply path

Claims (1)

原燃料を水蒸気改質により改質する改質部と、
シフト反応により、改質部で生成した改質ガスのＣＯ濃度を低減するＣＯ変成部としてのＣＯ低減部と、
前記改質部で生成した改質ガスと気化前の改質水との間で熱交換させることにより、前記改質水を加熱する気化前熱交換部と、
前記改質部の加熱に用いられる燃焼手段から排出される排ガスの熱を用いて、前記気化前熱交換部を経由した改質水を気化させる気化部と、
を備え、
前記気化部で生じた水蒸気が前記原燃料とともに前記改質部に供給され、
前記気化前熱交換部は、前記ＣＯ低減部に設けられ、
改質水の経路における前記ＣＯ低減部よりも上流側に設けられ、前記気化部に供給される改質水の圧力を減圧する減圧部と、
改質水の経路における前記減圧部よりも上流側に設けられ、前記ＣＯ低減部を経由した改質ガスと改質水との間で熱交換させることにより、前記改質水を加熱する熱交換部とをさらに備えることを特徴とする燃料電池用改質装置。 A reforming section for reforming raw fuel by steam reforming;
A CO reduction unit as a CO conversion unit that reduces the CO concentration of the reformed gas generated in the reforming unit by a shift reaction;
Heat exchange between the reformed gas generated in the reforming section and the reformed water before vaporization to heat the reformed water; and
A vaporization unit that vaporizes the reformed water that has passed through the pre-vaporization heat exchange unit using heat of exhaust gas discharged from the combustion means used for heating the reforming unit;
With
Water vapor generated in the vaporization unit is supplied to the reforming unit together with the raw fuel,
The pre-vaporization heat exchange unit is provided in the CO reduction unit,
A depressurization unit provided on the upstream side of the CO reduction unit in the path of the reforming water and depressurizing the pressure of the reforming water supplied to the vaporization unit ;
Heat exchange for heating the reformed water by exchanging heat between the reformed gas and the reformed water that is provided upstream of the decompression unit in the path of the reformed water and passes through the CO reducing unit. the reformer, characterized in that it further comprises a part.
JP2009110057A 2009-04-28 2009-04-28 Fuel cell reformer Expired - Fee Related JP5461880B2 (en)

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