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JP2005298249A - Reformed gas supply device and supply method - Google Patents

Reformed gas supply device and supply method Download PDF

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JP2005298249A
JP2005298249A JP2004114724A JP2004114724A JP2005298249A JP 2005298249 A JP2005298249 A JP 2005298249A JP 2004114724 A JP2004114724 A JP 2004114724A JP 2004114724 A JP2004114724 A JP 2004114724A JP 2005298249 A JP2005298249 A JP 2005298249A
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reformed gas
water
ammonia
steam
raw material
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Takeshi Kuwabara
武 桑原
Jun Ono
小野　　純
Shiro Fujishima
史郎 藤島
Shigeki Kobayashi
茂樹 小林
Yasushi Yoshino
靖 吉野
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T Rad Co Ltd
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    • 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
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Abstract

【課題】 アンモニアを含まない水素リッチな改質ガスを固体高分子型燃料電池に供給する低コストな改質ガス供給装置および供給方法の提供。
【解決手段】 改質ガス供給装置１０は、水蒸気発生器１１と、水蒸気発生器１１で得られた水蒸気と原料ガスを混合して原料−水蒸気混合物を生成する混合器１２と、混合器１２で得られた原料−水蒸気混合物を改質して水素リッチな改質ガスを生成する改質器１と、改質器１で得られた改質ガスを水と接触させ改質ガスに含まれているアンモニアを水に吸収させて除去するアンモニア除去器２と、アンモニア除去器２から流出するアンモニアを含む水を前記水蒸気発生器１１に補給水として供給する補給水供給手段１３を備えている。
【選択図】 図１
PROBLEM TO BE SOLVED: To provide a low-cost reformed gas supply apparatus and supply method for supplying a hydrogen-rich reformed gas not containing ammonia to a polymer electrolyte fuel cell.
A reformed gas supply device 10 includes a steam generator 11, a mixer 12 that mixes steam obtained by the steam generator 11 and a source gas to generate a raw material-steam mixture, and a mixer 12. The reformer 1 that reforms the obtained raw material-steam mixture to produce a hydrogen-rich reformed gas, and the reformed gas obtained in the reformer 1 is brought into contact with water and contained in the reformed gas. An ammonia remover 2 that absorbs and removes the ammonia that has been absorbed by water, and makeup water supply means 13 that supplies water containing ammonia flowing out from the ammonia remover 2 to the steam generator 11 as makeup water.
[Selection] Figure 1

Description

本発明は原料−水蒸気混合物を水蒸気改質し、得られた水素リッチな改質ガスを固体高分子型燃料電池に供給するように構成した改質ガス供給装置および供給方法に関する。   The present invention relates to a reformed gas supply apparatus and a supply method configured to steam reform a raw material-steam mixture and supply the obtained hydrogen-rich reformed gas to a polymer electrolyte fuel cell.

家庭に設置する発電用燃料電池や車搭載型の動力用燃料電池として固体高分子型燃料電池が有望視されている。固体高分子型燃料電池は高分子膜を用いた燃料電池であり、発電原料として供給される水素と酸素を反応して電力を発生するものである。一般にはメタン等の炭化水素からなる原料ガスと水蒸気の混合物を改質器に供給し、そこで水蒸気改質触媒の存在下に改質反応させ、生成した水素リッチな改質ガスを水素原料として固体高分子型燃料電池に供給する方式が多く採用されている。   Solid polymer fuel cells are promising as power generation fuel cells installed in homes and vehicle-mounted power fuel cells. A polymer electrolyte fuel cell is a fuel cell using a polymer membrane, and generates electricity by reacting hydrogen and oxygen supplied as a power generation raw material. In general, a mixture of raw material gas consisting of hydrocarbons such as methane and steam is supplied to the reformer, where it undergoes a reforming reaction in the presence of a steam reforming catalyst, and the resulting hydrogen-rich reformed gas is used as a hydrogen raw material as a solid. Many methods of supplying polymer type fuel cells are adopted.

固体高分子型燃料電池の寿命はその電極および高分子膜の劣化速度により決まる。従来から、電極および高分子膜を劣化させる主な要因は改質ガスに微量に含有する一酸化炭素（ＣＯ）によるものとされ、その対策として改質器の出口側に触媒を充填したＣＯ除去器を設け、改質ガスに微量に含まれるＣＯを除去している。しかし最近の研究によれば、電極および高分子膜の劣化はＣＯのほかに改質ガス中に微量に存在するアンモニアも影響することが分かってきた。   The life of a polymer electrolyte fuel cell is determined by the deterioration rate of its electrodes and polymer membrane. Conventionally, the main factor that deteriorates electrodes and polymer membranes has been attributed to carbon monoxide (CO) contained in a small amount in the reformed gas, and as a countermeasure, CO removal with a catalyst packed at the outlet of the reformer A device is provided to remove CO contained in a minute amount in the reformed gas. However, according to recent studies, it has been found that the deterioration of the electrode and the polymer film is affected by ammonia present in a minute amount in the reformed gas in addition to CO.

一般に、改質ガスを生成するために用いられるメタンやプロパン等の炭化水素系の原料ガスには窒素成分が含まれており、その窒素が改質器内で生成する水素と反応し、１／２Ｎ2 ＋３／２Ｈ2 ＝ＮＨ3 の反応式によりアンモニアが生成する。そして生成したアンモニアを含む改質ガスが固体高分子型燃料電池に供給されると、そのアンモニアにより電極および高分子膜が劣化する。 In general, a hydrocarbon-based raw material gas such as methane or propane used for generating a reformed gas contains a nitrogen component, and the nitrogen reacts with the hydrogen generated in the reformer, and 1 / Ammonia is produced by the reaction formula 2N 2 + 3 / 2H 2 = NH 3 . When the reformed gas containing the generated ammonia is supplied to the solid polymer fuel cell, the ammonia and the electrode and the polymer film deteriorate.

そこで、改質ガスに含まれるアンモニアをアンモニア除去器で除去してから固体高分子型燃料電池に供給する方法が特許文献１に提案されている。   Therefore, Patent Document 1 proposes a method of supplying ammonia to the polymer electrolyte fuel cell after removing ammonia contained in the reformed gas with an ammonia remover.

特開２００３−３１２４７号公報Japanese Patent Laid-Open No. 2003-31247

図３は特許文献１に記載された方法を実施するプロセスフロー図である。改質器１で生成したアンモニアを含む水素リッチな改質ガスは、配管ａを経てアンモニア除去器２に吹き込まれ、そこで上方から散水ノズル２ａで散布する水と接触させアンモニアを水に吸収して除去する。アンモニアを除去した改質ガスは配管ｂを経て固体高分子型燃料電池３に供給し、アンモニアを吸収した水は配管ｃを経て貯留槽４に排出する。   FIG. 3 is a process flow diagram for implementing the method described in Patent Document 1. The hydrogen-rich reformed gas containing ammonia generated in the reformer 1 is blown into the ammonia remover 2 through the pipe a, and is brought into contact with the water sprayed by the water spray nozzle 2a from above to absorb the ammonia in the water. Remove. The reformed gas from which ammonia has been removed is supplied to the polymer electrolyte fuel cell 3 via the pipe b, and the water that has absorbed ammonia is discharged to the storage tank 4 via the pipe c.

貯留槽４の貯留水は配管ｄに設けたポンプ５でイオン交換樹脂槽６に供給し、含まれているアンモニアをイオン交換樹脂に吸着させる。そしてアンモニアを除去した水を配管ｅで前記アンモニア除去器２の散水ノズル２ａに循環する。   The stored water in the storage tank 4 is supplied to the ion exchange resin tank 6 by the pump 5 provided in the pipe d, and the contained ammonia is adsorbed on the ion exchange resin. Then, the water from which ammonia has been removed is circulated through the pipe e to the watering nozzle 2a of the ammonia remover 2.

しかし前記した従来法では、アンモニアをイオン交換樹脂槽でイオン交換して除去するので、イオン交換樹脂槽を設置するスペースが必要となり、それに応じて設置コストが高くなるという問題がある。またアンモニアを吸着したイオン交換樹脂は定期的に再生もしくは交換する必要があり、運転コストの増加要因になる。そこで本発明は改質ガスからアンモニアを除去する従来技術における問題を解決することを課題とする。   However, in the above-described conventional method, ammonia is ion-exchanged and removed in the ion exchange resin tank, so that a space for installing the ion exchange resin tank is required, and there is a problem that the installation cost increases accordingly. Also, the ion exchange resin that has adsorbed ammonia must be periodically regenerated or replaced, which increases the operating cost. Therefore, an object of the present invention is to solve the problems in the prior art for removing ammonia from the reformed gas.

前記課題を達成する本発明の改質ガス供給装置は、固体高分子型燃料電池に水素リッチな改質ガスを供給する改質ガス供給装置である。そして本装置は、補給水を加熱して水蒸気を発生する水蒸気発生器と、水蒸気発生器で得られた水蒸気と原料ガスを混合して原料−水蒸気混合物を生成する混合器と、混合器で得られた原料−水蒸気混合物を改質して水素リッチな改質ガスを生成する改質器と、改質器で得られた改質ガスを水と接触させ、改質ガスに含まれているアンモニアを水に吸収して除去するアンモニア除去器と、アンモニア除去器から流出するアンモニアを含む水を前記水蒸気発生器に補給水として供給する補給水供給手段を備えていることを特徴とする（請求項１）。   The reformed gas supply apparatus of the present invention that achieves the above object is a reformed gas supply apparatus that supplies a hydrogen-rich reformed gas to a polymer electrolyte fuel cell. And this apparatus is obtained with a steam generator that heats make-up water to generate steam, a mixer that mixes the steam obtained by the steam generator and the source gas to produce a raw material-steam mixture, and a mixer. A reformer that reforms the obtained raw material-steam mixture to produce a hydrogen-rich reformed gas, and ammonia that is contained in the reformed gas by bringing the reformed gas obtained in the reformer into contact with water An ammonia remover that absorbs and removes water and water that contains ammonia flowing out from the ammonia remover is provided as make-up water supply means to the water vapor generator as make-up water. 1).

上記改質ガス供給装置において、前記アンモニア除去器は容器内に導入した改質ガスに上方から水を散布する水散布方式を採用できる（請求項２）。   In the reformed gas supply apparatus, the ammonia remover can employ a water spraying system in which water is sprayed from above onto the reformed gas introduced into the container.

また、前記課題を解決する本発明の改質ガス供給方法は、固体高分子型燃料電池に水素リッチな改質ガスを供給する改質ガス供給方法である。本方法は、補給水を加熱して水蒸気を発生し、その水蒸気と原料ガスを混合して原料−水蒸気混合物を生成し、その原料−水蒸気混合物を改質して水素リッチな改質ガスを生成し、得られた改質ガスを水と接触させて改質ガスに含まれるアンモニアを水に吸収して除去し、アンモニアを吸収した水を水蒸気発生用の補給水として循環することを特徴とする（請求項３）。   Moreover, the reformed gas supply method of the present invention that solves the above-mentioned problems is a reformed gas supply method for supplying a hydrogen-rich reformed gas to a polymer electrolyte fuel cell. This method heats make-up water to generate water vapor, mixes the water vapor and raw material gas to produce a raw material-steam mixture, and reforms the raw material-steam mixture to produce a hydrogen-rich reformed gas. Then, the obtained reformed gas is brought into contact with water to absorb and remove ammonia contained in the reformed gas, and the water that has absorbed ammonia is circulated as makeup water for generating steam. (Claim 3).

本発明の改質ガス供給装置によれば、アンモニアを含まない水素リッチな改質ガスを固体高分子型燃料電池に供給できる。また、アンモニア除去器から流出するアンモニアを含む水を水蒸気発生器に供給する補給水供給手段を備えているので、従来技術のようにアンモニアを吸着除去して定期的に系外に排出するためのイオン交換樹脂槽などの特別な装置を設ける必要がない。しかもアンモニアを含む補給水により発生した水蒸気にはアンモニア除去器から循環したアンモニアが含まれるが、そのアンモニア濃度は一定レベル以上にはならない。   According to the reformed gas supply apparatus of the present invention, a hydrogen-rich reformed gas containing no ammonia can be supplied to the solid polymer fuel cell. In addition, since it is provided with makeup water supply means for supplying water containing ammonia flowing out from the ammonia remover to the steam generator, the ammonia is adsorbed and removed as in the prior art and periodically discharged out of the system. There is no need to provide a special device such as an ion exchange resin tank. Moreover, although the water vapor generated from the makeup water containing ammonia contains ammonia circulated from the ammonia remover, the ammonia concentration does not exceed a certain level.

すなわちアンモニアを含む水蒸気と原料ガスが改質器に供給された場合、前記のように原料ガスに含まれる窒素が水素と反応して１／２Ｎ2 ＋３／２Ｈ2 ＝ＮＨ3 の反応式により新たなアンモニアが生成する。窒素から生成した新たなアンモニアは水蒸気発生器からの循環アンモニアと一緒になって改質器内のアンモニア濃度を増加させるが、アンモニアが平衡濃度以上になると可逆反応によりそれ以上にはならず、平衡濃度に落ち着く。このようにアンモニアが改質器−アンモニア除去器−水蒸気発生器−改質器の系統を循環する形態で系の運転を継続しても、アンモニア濃度が最大濃度になる改質器内においても平衡濃度以上にはならないので、改質系の運転を長期間安定に継続できる。 That is, when water vapor containing ammonia and a raw material gas are supplied to the reformer, nitrogen contained in the raw material gas reacts with hydrogen as described above, and a new reaction formula of 1 / 2N 2 + 3 / 2H 2 = NH 3 is obtained. Ammonia is produced. New ammonia generated from nitrogen increases the ammonia concentration in the reformer together with the circulating ammonia from the steam generator. However, when ammonia exceeds the equilibrium concentration, it does not increase further due to the reversible reaction. Settle to concentration. Thus, even if the system operation is continued in such a form that ammonia circulates through the system of the reformer-ammonia remover-steam generator-reformer, it is balanced even in the reformer where the ammonia concentration reaches the maximum concentration. Since it does not exceed the concentration, the operation of the reforming system can be stably continued for a long time.

上記改質ガス供給装置において、前記請求項２のように、アンモニア除去器として容器内に導入した改質ガスに上方から水を散布する水散布方式を採用する場合は、簡単な構造で効率の良いアンモニア除去器を構成できる。   In the above reformed gas supply apparatus, when adopting a water spraying method in which water is sprayed from above onto the reformed gas introduced into the container as an ammonia remover, the efficiency can be improved with a simple structure. A good ammonia remover can be constructed.

本発明の改質ガス供給方法によれば、アンモニアを含まない水素リッチな改質ガスを効率よく固体高分子型燃料電池に供給できるとともに、補給水として循環するアンモニア濃度がその平衡濃度以上にはならないので、改質系の運転を長期間安定に継続できる。   According to the reformed gas supply method of the present invention, the hydrogen-rich reformed gas containing no ammonia can be efficiently supplied to the polymer electrolyte fuel cell, and the concentration of ammonia circulating as make-up water exceeds the equilibrium concentration. Therefore, the operation of the reforming system can be stably continued for a long time.

次に図面により本発明を実施するための最良の形態を説明する。図１は本発明の改質ガス供給装置のプロセスフロー図である。改質ガス供給装置１０は、補給水を加熱して水蒸気を発生する水蒸気発生器１１と、水蒸気発生器１１で得られた水蒸気と原料ガスを混合して原料−水蒸気混合物を生成する混合器１２と、混合器１２で得られた原料−水蒸気混合物を改質して水素リッチな改質ガスを生成する改質器１と、改質器１で得られた改質ガスを水と接触させ、改質ガスに含まれているアンモニアを水に吸収して除去するアンモニア除去器２と、アンモニア除去器２から流出するアンモニアを含む水を前記水蒸気発生器１１に補給水として供給する補給水供給手段１３を備えている。   Next, the best mode for carrying out the present invention will be described with reference to the drawings. FIG. 1 is a process flow diagram of the reformed gas supply apparatus of the present invention. The reformed gas supply apparatus 10 includes a water vapor generator 11 that heats makeup water to generate water vapor, and a mixer 12 that mixes the water vapor obtained by the water vapor generator 11 and a raw material gas to produce a raw material-steam mixture. A reformer 1 that reforms the raw material-steam mixture obtained in the mixer 12 to produce a hydrogen-rich reformed gas, and the reformed gas obtained in the reformer 1 is brought into contact with water, Ammonia remover 2 that absorbs and removes ammonia contained in the reformed gas by water, and makeup water supply means that supplies the water containing ammonia flowing out from ammonia remover 2 to makeup generator 11 as makeup water 13 is provided.

水蒸気発生器１１は配管ｆから供給される気体または液体燃料を燃焼するバーナ等の燃焼部１４と、補給水を加熱して水蒸気を生成する水蒸気発生部１５を備えている。水蒸気発生部１５には補給水供給手段１３からの補給水を受け入れる配管ｉと、発生した水蒸気を混合器１２に供給する配管ｇが接続される。   The steam generator 11 includes a combustion section 14 such as a burner that burns gas or liquid fuel supplied from the pipe f, and a steam generation section 15 that generates steam by heating makeup water. A pipe i for receiving makeup water from the makeup water supply means 13 and a pipe g for supplying the generated steam to the mixer 12 are connected to the steam generation section 15.

水蒸気と原料ガスを混合して原料−水蒸気混合物を生成する混合器１２は、例えば水蒸気の吸引力により炭化水素系の原料ガスを吸引するエジェクター式の混合器を使用することができる。エジェクター式の混合器は特別な動力源を必要としないので装置をコンパクト化できるという有利性がある。   As the mixer 12 that mixes water vapor and raw material gas to produce a raw material-water vapor mixture, for example, an ejector-type mixer that sucks a hydrocarbon-based raw material gas by the suction force of water vapor can be used. The ejector-type mixer does not require a special power source, and thus has an advantage that the apparatus can be made compact.

改質器１としては、原料ガスを水蒸気と酸素の存在下に自己酸化すると共に水蒸気改質を行って水素リッチな改質ガスを生成する自己酸化内部加熱型の改質器１を使用することができる。自己酸化内部加熱型の改質器１には、単一の反応容器内に水蒸気改質触媒と酸化触媒を混合した混合触媒層と、混合触媒層の下流側に配置したシフト触媒層を設けたものがある。また外反応室と内反応室を有する二重筒型の自己酸化内部加熱型の改質器１を採用することもでき、その場合には外反応室に水蒸気触媒層を設け、内反応室に単一型と同様な混合触媒層とシフト触媒槽を設ける。   As the reformer 1, use a self-oxidation internal heating type reformer 1 that self-oxidizes the raw material gas in the presence of steam and oxygen and performs steam reforming to generate a hydrogen-rich reformed gas. Can do. The reformer 1 of the self-oxidation internal heating type is provided with a mixed catalyst layer in which a steam reforming catalyst and an oxidation catalyst are mixed in a single reaction vessel, and a shift catalyst layer disposed on the downstream side of the mixed catalyst layer. There is something. In addition, a double-cylinder self-oxidation internal heating type reformer 1 having an outer reaction chamber and an inner reaction chamber can be employed. In this case, a steam catalyst layer is provided in the outer reaction chamber, A mixed catalyst layer and shift catalyst tank similar to the single type are provided.

混合触媒層に含まれる酸化触媒は、原料−水蒸気混合物の原料ガスと配管ｊから導入する酸素含有ガス（一般には空気）の酸素と反応させ、その反応熱で混合触媒層の温度を改質反応温度である７００℃付近まで昇温するものである。そして混合触媒層に含まれる水蒸気触媒の触媒作用により、前記改質反応温度条件下で原料ガスと水蒸気が反応して水素リッチな改質ガスを生成する。なおシフト触媒層は改質ガスに僅かに含まれる一酸化炭素（ＣＯ）をシフト反応により低減するものである。   The oxidation catalyst contained in the mixed catalyst layer reacts with the raw material gas of the raw material-steam mixture and oxygen of the oxygen-containing gas (generally air) introduced from the pipe j, and the reaction heat changes the temperature of the mixed catalyst layer. The temperature is raised to around 700 ° C. which is the temperature. Then, by the catalytic action of the steam catalyst contained in the mixed catalyst layer, the raw material gas reacts with the steam under the reforming reaction temperature condition to generate a hydrogen-rich reformed gas. The shift catalyst layer reduces carbon monoxide (CO) slightly contained in the reformed gas by a shift reaction.

二重筒型の自己酸化内部加熱型の改質器１を採用した場合には、原料−水蒸気混合物を外反応室に導入し、そこで水蒸気改質触媒により予備的な水蒸気改質を行って原料ガスの一部を水素リッチな改質ガスに変換し、未反応の原料ガスを含む残りの原料−水蒸気混合物を内反応室に送り、そこで残った原料ガスを水蒸気改質する。   When the double-cylinder self-oxidation internal heating type reformer 1 is employed, the raw material-steam mixture is introduced into the outer reaction chamber, where preliminary steam reforming is performed by a steam reforming catalyst to provide the raw material. A part of the gas is converted into a hydrogen-rich reformed gas, the remaining raw material-steam mixture containing unreacted source gas is sent to the inner reaction chamber, and the remaining source gas is steam reformed there.

原料ガスとしてメタン等の炭化水素を使用する場合には、前記のように炭化水素に含まれる窒素が改質器１内で水素と反応しアンモニアを生成する。なお、内部加熱型改質器の場合には、自己酸化用空気に含まれるＮ2 からもアンモニアが生成される。そのため改質器１から配管ａに流出するアンモニアを含む改質ガスをアンモニア除去器２の下方に吹き込み、散水ノズル２ａで上方から散布する水と接触させ、アンモニアを水に吸収して除去する。アンモニアを含まない改質ガスは配管ｂを経て固体高分子型燃料電池３に供給され、アンモニアを吸収した水はアンモニア除去器２の下部に落下して滞留する。なお散水ノズル２ａには外部から純水等の散布水（洗浄水）を供給する配管ｋが接続される。 When a hydrocarbon such as methane is used as the source gas, nitrogen contained in the hydrocarbon reacts with hydrogen in the reformer 1 to generate ammonia as described above. In the case of the internal heating type reformer, ammonia is also generated from N 2 contained in the autooxidation air. Therefore, the reformed gas containing ammonia flowing out from the reformer 1 to the pipe a is blown below the ammonia remover 2 and brought into contact with water sprayed from above by the water spray nozzle 2a, and the ammonia is absorbed and removed by the water. The reformed gas that does not contain ammonia is supplied to the polymer electrolyte fuel cell 3 via the pipe b, and the water that has absorbed ammonia falls to the lower part of the ammonia remover 2 and stays there. A pipe k for supplying spray water (wash water) such as pure water from the outside is connected to the water spray nozzle 2a.

アンモニア除去器２の下部に滞留するアンモニアを含む水は、補給水供給手段１３により前記水蒸気発生器１１の水蒸気発生部１５に補給水として供給する。補給水供給手段１３は配管ｉと、配管ｉに設けたポンプ１６を備えており、配管ｉの途中に外部から純水等の新しい水を補給する配管ｌが合流し、その配管ｌに調整弁１７が設けられる。   The water containing ammonia staying in the lower part of the ammonia remover 2 is supplied as make-up water to the steam generating section 15 of the steam generator 11 by the make-up water supply means 13. The makeup water supply means 13 includes a piping i and a pump 16 provided in the piping i. A piping l for replenishing new water such as pure water from the outside joins the piping i, and a regulating valve is connected to the piping l. 17 is provided.

次に図１の改質ガス供給装置１０により固体高分子型燃料電池に改質ガスを供給する方法を説明する。先ず各機器の運転準備をし、配管ｌから所定量の純水を水蒸気発生器１１に供給する。次に燃料を燃焼部１４に供給して燃焼し、水蒸気発生部１５の水を加熱して水蒸気を発生する。発生した水蒸気は配管ｇから混合器１２に供給され、そこで配管ｍから供給される原料ガス（炭化水素系ガス）と混合する。   Next, a method for supplying reformed gas to the polymer electrolyte fuel cell by the reformed gas supply apparatus 10 of FIG. 1 will be described. First, each device is prepared for operation, and a predetermined amount of pure water is supplied from the pipe l to the steam generator 11. Next, fuel is supplied to the combustion unit 14 and combusted, and water in the water vapor generation unit 15 is heated to generate water vapor. The generated water vapor is supplied from the pipe g to the mixer 12, where it is mixed with the raw material gas (hydrocarbon gas) supplied from the pipe m.

混合器１２から流出する原料−水蒸気混合物は配管ｈを経て改質器１に供給され、そこで水蒸気改質により得られた改質ガスが配管ａを経てアンモニア除去器２の下部に供給される。アンモニア除去器２に吹き込まれた改質ガスは上方から散水ノズル２ａによって散布される水と接触し、含まれているアンモニアを水に吸収して除去する。   The raw material-steam mixture flowing out from the mixer 12 is supplied to the reformer 1 through the pipe h, and the reformed gas obtained by steam reforming is supplied to the lower part of the ammonia remover 2 through the pipe a. The reformed gas blown into the ammonia remover 2 comes into contact with the water sprayed by the watering nozzle 2a from above, and the contained ammonia is absorbed by the water and removed.

アンモニアが除去された改質ガスは配管ｂを経て固体高分子型燃料電池３に供給し、アンモニアを含む滞留水はポンプ１６により配管ｃを経て前記水蒸気発生部１５に循環する。水蒸気発生部１５には図示しない液面計が設けられ、その液面が予め設定された値になるように制御装置（図示せず）が配管ｌに設けた調整弁１７を制御し、補給水の供給量を調整する。   The reformed gas from which the ammonia has been removed is supplied to the polymer electrolyte fuel cell 3 through the pipe b, and the accumulated water containing ammonia is circulated to the water vapor generating unit 15 through the pipe c by the pump 16. The water vapor generation unit 15 is provided with a liquid level gauge (not shown), and a control device (not shown) controls the adjustment valve 17 provided in the pipe l so that the liquid level becomes a preset value, thereby supplying makeup water. Adjust the supply amount.

上記プロセスでは、改質器１の内部で原料ガスに含まれている窒素と水素の反応により生成したアンモニアが系内を循環する。しかし前述のように改質器１の内部におけるアンモニアの生成反応は平衡反応であるため、系内のアンモニア濃度は平衡濃度以上にはならない。アンモニアの平衡濃度は水蒸気改質反応等の条件によっても多少変化するが、通常１０〜５０ppm 程度であり、この範囲であれば改質器１の運転に支障をきたすことはない。なお、本発明のアンモニア除去器としては、容器内の水に改質ガスを通すバブリング方式のものあるいは、改質ガスを冷却することにより改質ガス中の水蒸気を凝縮させ、この凝縮水中にアンモニアを溶解させる方式のものであってもよい。また、以上の説明は、自己酸化内部加熱型の改質器により、改質ガスが供給される例をとったが、本発明の改質ガスの供給装置は外熱式の改質器を用いてもよい。   In the above process, ammonia generated by the reaction of nitrogen and hydrogen contained in the raw material gas inside the reformer 1 circulates in the system. However, as described above, the ammonia production reaction inside the reformer 1 is an equilibrium reaction, and therefore the ammonia concentration in the system does not exceed the equilibrium concentration. Although the equilibrium concentration of ammonia varies somewhat depending on conditions such as the steam reforming reaction, it is usually about 10 to 50 ppm. Within this range, the operation of the reformer 1 is not hindered. The ammonia remover of the present invention may be a bubbling type that passes the reformed gas through the water in the container, or water vapor in the reformed gas is condensed by cooling the reformed gas, and the condensed water contains ammonia. It may be of a system that dissolves In the above description, the reformed gas is supplied by the self-oxidation internal heating type reformer. However, the reformed gas supply device of the present invention uses an external heating type reformer. May be.

次に、図２は本発明の改質ガス供給装置の第２の実施の形態を示すプロセスフロー図である。この装置が前記図１のそれと異なる点は、アンモニア除去器２の下部と散水ノズル２ａとの間をポンプ２１を介して配管ｋで連結したこと、アンモニア除去器２の下端に接続された配管ｃ中に、貯水槽２２を設けると共に、その貯水槽２２とアンモニア除去器２とを連結する配管に給水用の配管ｌを接続し、その接続点の上流側と下流側に夫々調整弁１７，１８，２０を設けたことである。
そして水蒸気発生器１１には、貯水槽２２からポンプ１６を介して補給水を供給する。 Next, FIG. 2 is a process flow diagram showing a second embodiment of the reformed gas supply apparatus of the present invention. 1 differs from that of FIG. 1 in that the lower part of the ammonia remover 2 and the watering nozzle 2a are connected by a pipe k via a pump 21 and a pipe c connected to the lower end of the ammonia remover 2. A water tank 22 is provided therein, and a water supply pipe 1 is connected to a pipe connecting the water tank 22 and the ammonia remover 2, and the regulating valves 17, 18 are respectively connected upstream and downstream of the connection point. , 20 are provided.
The water vapor generator 11 is supplied with makeup water from the water storage tank 22 via the pump 16.

また、アンモニア除去器２の下部に滞留する水は、通常運転時にポンプ２１を介して循環する。その循環によるアンモニアを含む水は、後述する工程で貯水槽２２を介して補給水供給手段１３により前記水蒸気発生器１１の水蒸気発生部１５に補給水として供給される。この例の補給水供給手段１３は配管ｉと、配管ｉに設けた調整弁１９およびポンプ１６並びに貯水槽２２を備えており、貯水槽２２には外部から純水等の新しい水を補給する配管ｌが設けられ、その配管ｌに調整弁１７が設けられる。なお、貯水槽２２は図示しないレベル計によりその水位が常に計測され、それが下限レベル以下になったときには、調整弁１７および調整弁２０が開となり、配管ｌより純水等が給水され、上限レベルで給水が停止される。   Further, the water staying in the lower part of the ammonia remover 2 is circulated through the pump 21 during normal operation. The water containing ammonia by the circulation is supplied as make-up water to the water vapor generating part 15 of the water vapor generator 11 by the make-up water supply means 13 through the water storage tank 22 in a process described later. The make-up water supply means 13 of this example includes a pipe i, a regulating valve 19 provided in the pipe i, a pump 16 and a water storage tank 22. The water supply tank 22 is supplied with new water such as pure water from the outside. l is provided, and a regulating valve 17 is provided in the pipe l. In addition, the water level of the water storage tank 22 is always measured by a level meter (not shown). When the water level is lower than the lower limit level, the regulating valve 17 and the regulating valve 20 are opened, and pure water or the like is supplied from the pipe l, and the upper limit is reached. Water supply is stopped at the level.

次に図２の改質ガス供給装置１０により固体高分子型燃料電池に改質ガスを供給する方法を説明する。先ず各機器の運転準備をし、貯水槽２２から調整弁１９およびポンプ１６を介して、流量調整された所定量の純水を水蒸気発生器１１に供給すると共に、燃料を燃焼部１４に供給して燃焼し、水蒸気発生部１５の水を加熱して水蒸気を発生する。その後の作用は、図１の例と同一である。そして、アンモニア除去器２に吹き込まれた改質ガスは上方から散水ノズル２ａによって散布された水と接触して、改質ガス中に含まれているアンモニアを水に吸収して除去する。このとき、アンモニア除去器２の底部と散水ノズル２ａとの間を連結する配管ｋ中のポンプ２１が駆動され、流量が調整されて、アンモニアを含む水が循環する。このとき、アンモニア除去器２の底に連通する配管ｃの調整弁１８は閉とされる。アンモニアが除去された改質ガスは配管ｂを経て固体高分子型燃料電池３に供給される。   Next, a method for supplying the reformed gas to the polymer electrolyte fuel cell by the reformed gas supply apparatus 10 of FIG. 2 will be described. First, each device is prepared for operation, and a predetermined amount of pure water whose flow rate is adjusted is supplied from the water storage tank 22 to the steam generator 11 through the adjustment valve 19 and the pump 16, and fuel is supplied to the combustion unit 14. Then, the water in the steam generation unit 15 is heated to generate steam. The subsequent operation is the same as in the example of FIG. Then, the reformed gas blown into the ammonia remover 2 comes into contact with the water sprayed by the watering nozzle 2a from above, and the ammonia contained in the reformed gas is absorbed into the water and removed. At this time, the pump 21 in the pipe k connecting the bottom of the ammonia remover 2 and the watering nozzle 2a is driven, the flow rate is adjusted, and water containing ammonia circulates. At this time, the regulating valve 18 of the pipe c communicating with the bottom of the ammonia remover 2 is closed. The reformed gas from which the ammonia has been removed is supplied to the polymer electrolyte fuel cell 3 through the pipe b.

所定時間、上記運転が継続された後、本装置が停止されると、運転再開の準備工程に入る。先ず、調整弁１８，２０が開、調整弁１７，１９が閉となり、アンモニア除去器２の底部のアンモニアを含む貯留水が貯水槽２２に回収される。次に、調整弁２０が閉、調整弁１８，１７が開となり、アンモニア除去器２の底部に新しい水が供給される。その結果、アンモニア除去器２の底部にはアンモニアを含まない初期状態の水が保持される。その後、調整弁１８，１７，２０が閉となる。
次いで、運転が再開されると、貯水槽２２中のアンモニアを含む滞留水がポンプ１６により配管ｉを経て前記水蒸気発生部１５に供給され、前記工程が繰り返される。 After the operation has been continued for a predetermined time, when the apparatus is stopped, a preparation process for restarting the operation is started. First, the regulating valves 18 and 20 are opened, the regulating valves 17 and 19 are closed, and the stored water containing ammonia at the bottom of the ammonia removing device 2 is collected in the water tank 22. Next, the regulating valve 20 is closed, the regulating valves 18 and 17 are opened, and new water is supplied to the bottom of the ammonia removing device 2. As a result, water in the initial state not containing ammonia is held at the bottom of the ammonia remover 2. Thereafter, the regulating valves 18, 17 and 20 are closed.
Next, when the operation is resumed, the stagnant water containing ammonia in the water storage tank 22 is supplied to the water vapor generating unit 15 through the pipe i by the pump 16, and the above process is repeated.

上記図２のプロセスでも、改質器１の内部で原料ガスに含まれている窒素と水素の反応により生成したアンモニアが系内を循環する。しかし前述のように改質器１の内部におけるアンモニアの生成反応は平衡反応であるため、系内のアンモニア濃度は平衡濃度以上にはならない。   Also in the process of FIG. 2, the ammonia produced by the reaction of nitrogen and hydrogen contained in the raw material gas inside the reformer 1 circulates in the system. However, as described above, the ammonia production reaction inside the reformer 1 is an equilibrium reaction, and therefore the ammonia concentration in the system does not exceed the equilibrium concentration.

本発明の改質ガス供給装置および供給方法は、炭化水素を水蒸気改質して得られる改質ガスを固体高分子型燃料電池に供給する装置および方法として利用できる。   The reformed gas supply apparatus and supply method of the present invention can be used as an apparatus and method for supplying a reformed gas obtained by steam reforming hydrocarbons to a polymer electrolyte fuel cell.

本発明の改質ガス供給装置のプロセスフロー図。The process flow figure of the reformed gas supply apparatus of this invention. 本発明の改質ガス供給装置の他のプロセスフロー図。The other process flow figure of the reformed gas supply apparatus of this invention. 従来の改質ガス供給装置のプロセスフロー図。The process flow figure of the conventional reformed gas supply apparatus.

符号の説明Explanation of symbols

１ 改質器
２ アンモニア除去器
２ａ 散水ノズル
３ 固体高分子型燃料電池
４ 貯留槽
５ ポンプ
６ イオン交換樹脂槽
１０ 改質ガス供給装置
１１ 水蒸気発生器
１２ 混合器 DESCRIPTION OF SYMBOLS 1 Reformer 2 Ammonia remover 2a Sprinkling nozzle 3 Solid polymer fuel cell 4 Storage tank 5 Pump 6 Ion exchange resin tank 10 Reformed gas supply apparatus 11 Water vapor generator 12 Mixer

１３ 補給水供給手段
１４ 燃焼部
１５ 水蒸気発生部
１６ ポンプ
１７ 調整弁
１８ 調整弁
１９ 調整弁
２０ 調整弁
２１ ポンプ
２２ 貯水槽
ａ〜ｍ 配管
DESCRIPTION OF SYMBOLS 13 Supply water supply means 14 Combustion part 15 Water vapor generation part 16 Pump 17 Adjustment valve 18 Adjustment valve 19 Adjustment valve 20 Adjustment valve 21 Pump 22 Water storage tank am

Claims (3)

固体高分子型燃料電池に水素リッチな改質ガスを供給する改質ガス供給装置において、補給水を加熱して水蒸気を発生する水蒸気発生器１１と、水蒸気発生器１１で得られた水蒸気と原料ガスを混合して原料−水蒸気混合物を生成する混合器１２と、混合器１２で得られた原料−水蒸気混合物を改質して水素リッチな改質ガスを生成する改質器１と、改質器１で得られた改質ガスを水と接触させ改質ガスに含まれているアンモニアを水に吸収させて除去するアンモニア除去器２と、アンモニア除去器２から流出するアンモニアを含む水を前記水蒸気発生器１１に補給水として供給する補給水供給手段１３を備えていることを特徴とする改質ガス供給装置。   In a reformed gas supply device that supplies hydrogen-rich reformed gas to a polymer electrolyte fuel cell, a steam generator 11 that heats makeup water to generate steam, and steam and raw material obtained by the steam generator 11 A mixer 12 for mixing a gas to produce a raw material-steam mixture; a reformer 1 for reforming the raw material-steam mixture obtained by the mixer 12 to produce a hydrogen-rich reformed gas; An ammonia remover 2 for removing the ammonia contained in the reformed gas by contacting the reformed gas obtained in the vessel 1 with water, and water containing ammonia flowing out from the ammonia remover 2 A reformed gas supply device comprising supply water supply means 13 for supplying the water vapor generator 11 as makeup water. 請求項１において、前記アンモニア除去器２は容器内に導入した改質ガスに上方から水を散布する水散布方式とされることを特徴とする改質ガス供給装置。   2. The reformed gas supply apparatus according to claim 1, wherein the ammonia remover is of a water spraying system in which water is sprayed from above onto the reformed gas introduced into the container. 固体高分子型燃料電池に水素リッチな改質ガスを供給する改質ガス供給方法において、補給水を加熱して水蒸気を発生し、その水蒸気と原料ガスを混合して原料−水蒸気混合物を生成し、その原料−水蒸気混合物を改質して水素リッチな改質ガスを生成し、得られた改質ガスに水を接触して改質ガスに含まれるアンモニアを水側に吸収して除去し、アンモニアを吸収した水を水蒸気発生用の補給水として循環することを特徴とする改質ガス供給方法。
In a reformed gas supply method for supplying a hydrogen-rich reformed gas to a polymer electrolyte fuel cell, the makeup water is heated to generate steam, and the steam and the source gas are mixed to form a source-steam mixture. , Reforming the raw material-steam mixture to produce a hydrogen-rich reformed gas, contacting the obtained reformed gas with water to absorb and remove ammonia contained in the reformed gas on the water side, A reformed gas supply method comprising circulating water that has absorbed ammonia as makeup water for generating steam.
JP2004114724A 2004-04-08 2004-04-08 Reformed gas supply device and supply method Pending JP2005298249A (en)

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