JP5165832B2 - Hydrogen generating apparatus and method - Google Patents

Hydrogen generating apparatus and method Download PDF

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JP5165832B2
JP5165832B2 JP2005020910A JP2005020910A JP5165832B2 JP 5165832 B2 JP5165832 B2 JP 5165832B2 JP 2005020910 A JP2005020910 A JP 2005020910A JP 2005020910 A JP2005020910 A JP 2005020910A JP 5165832 B2 JP5165832 B2 JP 5165832B2
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久尚 城
英明 松田
秀史 赤阪
一夫 道谷
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    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288Evaporation of one or more of the different feed components
    • C01B2203/1294Evaporation by heat exchange with hot process stream
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    • C01B2203/14Details of the flowsheet
    • C01B2203/142At least two reforming, decomposition or partial oxidation steps in series
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • YGENERAL 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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Description

本発明は、天然ガス,プロパンガス,ガソリン,ナフサ,灯油,メタノール,バイオガス等の炭化水素系化合物ガスと水ならびに空気もしくは酸素を原料とし、燃料電池等の水素利用機器に対して水素を供給するための水素発生装置および方法に関するものである。   The present invention uses hydrocarbon compound gas such as natural gas, propane gas, gasoline, naphtha, kerosene, methanol, biogas and water and air or oxygen as raw materials to supply hydrogen to hydrogen-using equipment such as fuel cells. The present invention relates to a hydrogen generation apparatus and method.

化石燃料に替わるエネルギー源の有力候補の一つとして、水素が注目されているが、その有効利用のためには水素パイプライン等の社会インフラの整備が必要とされている。その一つの方法として、天然ガス、その他化石燃料、アルコール等の現状既に構築されている運送、搬送などのインフラを利用し、水素を必要とする場所でそれら燃料を改質して水素を発生させる方法が検討されている。   Hydrogen is attracting attention as one of the promising energy sources to replace fossil fuels, but social infrastructure such as hydrogen pipelines is required for its effective use. One way to do this is to use natural gas, other fossil fuels, alcohol, and other infrastructure that has already been built, such as transportation and transportation, and reform the fuel where hydrogen is needed to generate hydrogen. A method is being considered.

上記のような水素発生装置として、例えば下記の特許文献1に示すものが開示されている。この水素発生装置は、炭化水素ガスと水蒸気の混合ガスを原料として改質器に導入し、触媒による改質反応によって得られた水素リッチな改質ガスから水素ガスを分離精製するものである。この水素発生装置は、改質反応が吸熱反応であることから、改質器にバーナーを備え、改質反応に必要な熱エネルギーを外部から供給している。
特開2002−53307号公報
As the hydrogen generator as described above, for example, one disclosed in Patent Document 1 below is disclosed. This hydrogen generator introduces a mixed gas of hydrocarbon gas and steam into a reformer as a raw material, and separates and purifies hydrogen gas from hydrogen-rich reformed gas obtained by a reforming reaction using a catalyst. In this hydrogen generator, since the reforming reaction is an endothermic reaction, the reformer is equipped with a burner and supplies the heat energy necessary for the reforming reaction from the outside.
JP 2002-53307 A

しかしながら、上記特許文献1の水素発生装置では、改質器周囲にバーナーを備えた加熱炉を設ける必要があるため、改質器自体の構造が複雑になるとともに、耐熱性や耐圧性を持たせる構造も複雑になり、設備コストが高くなるうえ、メンテナンスにも手間とコストを要するという問題がある。また、改質反応に必要な熱エネルギーを外部から供給することから、熱効率も悪く、エネルギーコストも高くなり、さらに窒素酸化物や硫黄酸化物が発生するという問題がある。   However, in the hydrogen generator of Patent Document 1, since it is necessary to provide a heating furnace equipped with a burner around the reformer, the structure of the reformer itself is complicated, and heat resistance and pressure resistance are provided. There are problems that the structure is complicated, the equipment cost is high, and the maintenance requires labor and cost. In addition, since heat energy necessary for the reforming reaction is supplied from the outside, there is a problem that heat efficiency is poor, energy cost is increased, and nitrogen oxides and sulfur oxides are generated.

本発明は、このような問題を解決するためになされたものであり、エネルギー効率に優れるとともに、設備コストも節減できる水素発生装置および方法を提供することを目的とする。   The present invention has been made to solve such a problem, and an object of the present invention is to provide a hydrogen generation apparatus and method that are excellent in energy efficiency and can reduce facility costs.

上記目的を達成するため、本発明の水素発生装置は、炭化水素系ガスを改質して水素リッチな改質ガスを生成する水素発生装置であって、
上記炭化水素系ガスを水蒸気および酸素とともに触媒と接触反応させて炭化水素ガスの燃焼と改質とを行う改質器を備え、
上記改質器の下流側に設けられた改質ガス路には、
改質ガスとの熱交換により、水蒸気源としての水を加熱する水加熱用熱交換器と、
改質ガスとの熱交換により、炭化水素系ガスを加熱する炭化水素系ガス加熱用熱交換器が設けられ、
さらに、上記改質ガス路における水加熱用熱交換器および炭化水素系ガス加熱用熱交換器の上流側に、改質ガスとの熱交換により、上記炭化水素系ガス加熱用熱交換器で加熱された炭化水素系ガスと水加熱用熱交換器で加熱された水から得られた水蒸気との混合ガスである原料ガスを加熱する原料ガス加熱用熱交換器が設けられ、
さらに、上記原料ガスを供給する原料ガス供給路には、改質器が充分に温度上昇していない水素発生装置の稼動初期において、改質器に導入する原料ガスを加熱する原料ヒータが設けられ
上記水加熱用熱交換器、炭化水素系ガス加熱用熱交換器、原料ガス加熱用熱交換器および原料ヒータには酸素ガスを導入せずに、原料ガス供給路に酸素ガスを導入することを要旨とする。
To achieve the above object, the hydrogen generator of the present invention is a hydrogen generator that reforms a hydrocarbon-based gas to produce a hydrogen-rich reformed gas,
Comprising a reformer that causes the hydrocarbon gas to contact and react with the catalyst together with water vapor and oxygen to burn and reform the hydrocarbon gas;
In the reformed gas path provided on the downstream side of the reformer,
A heat exchanger for water heating that heats water as a water vapor source by heat exchange with the reformed gas;
A heat exchanger for heating a hydrocarbon gas that heats the hydrocarbon gas by heat exchange with the reformed gas is provided,
Further, heating with the hydrocarbon gas heating heat exchanger is performed upstream of the water heating heat exchanger and the hydrocarbon gas heating heat exchanger in the reformed gas path by heat exchange with the reformed gas. A raw material gas heating heat exchanger for heating a raw material gas that is a mixed gas of the hydrocarbon-based gas and water vapor obtained from water heated by the water heating heat exchanger,
Further, the raw material gas supply path for supplying the raw material gas is provided with a raw material heater for heating the raw material gas introduced into the reformer in the initial operation of the hydrogen generator in which the temperature of the reformer has not sufficiently increased. ,
The water-heating heat exchanger, hydrocarbon gas heat exchanger for heating, without introducing oxygen gas into the heat exchanger and the raw material for the heater material gas heating, Rukoto to introduce oxygen gas into the raw material gas supply passage Is the gist.

また、上記目的を達成するため、本発明の水素発生方法は、炭化水素系ガスを改質して水素リッチな改質ガスを生成する水素発生方法であって、
上記炭化水素系ガスを水蒸気および酸素とともに触媒と接触反応させて炭化水素ガスの燃焼と改質とを行う改質工程と、
上記改質工程の下流側において、
改質ガスとの熱交換により、水蒸気源としての水を加熱する水加熱用熱交換工程と、
改質ガスとの熱交換により、炭化水素系ガスを加熱する炭化水素系ガス加熱用熱交換工程を行ない、
さらに、上記改質ガス路における水加熱用熱交換工程および炭化水素系ガス加熱用熱交換工程の上流側において、改質ガスとの熱交換により、上記炭化水素系ガス加熱用熱交換工程で加熱された炭化水素系ガスと水加熱用熱交換工程で加熱された水から得られた水蒸気との混合ガスである原料ガスを加熱する原料ガス加熱用熱交換工程を行い、
さらに、上記原料ガスを供給する原料ガス供給段階において、改質器が充分に温度上昇していない水素発生装置の稼動初期において、改質器に導入する原料ガスを加熱する原料加熱工程を行い、
上記水加熱用熱交換工程、炭化水素系ガス加熱用熱交換工程、原料ガス加熱用熱交換工程および原料加熱工程では酸素ガスを導入せずに、上記原料ガス供給段階において酸素ガスを導入することを要旨とする。
In order to achieve the above object, the hydrogen generation method of the present invention is a hydrogen generation method for reforming a hydrocarbon gas to generate a hydrogen-rich reformed gas,
A reforming step of bringing the hydrocarbon gas into contact with a catalyst together with water vapor and oxygen to burn and reform the hydrocarbon gas;
On the downstream side of the reforming step,
A heat exchange process for water heating that heats water as a water vapor source by heat exchange with the reformed gas;
A heat exchange process for heating a hydrocarbon gas that heats the hydrocarbon gas by heat exchange with the reformed gas,
Further, heating is performed in the hydrocarbon gas heating heat exchange step by heat exchange with the reformed gas upstream of the water heating heat exchange step and the hydrocarbon gas heating heat exchange step in the reformed gas path. Performing a raw material gas heating heat exchange step of heating a raw material gas which is a mixed gas of the hydrocarbon-based gas and water vapor obtained from the water heated in the water heating heat exchange step,
Further, the raw material gas supply step of supplying the raw material gas, the operation initial hydrogen generator reformer is not sufficiently rise in temperature, line physician raw material heating step of heating the raw material gas to be introduced into the reformer ,
Introducing oxygen gas in the raw material gas supply step without introducing oxygen gas in the water heating heat exchange step, hydrocarbon gas heating heat exchange step, raw material gas heating heat exchange step and raw material heating step Is the gist.

本発明は、改質器において上記炭化水素系ガスを水蒸気および酸素とともに触媒と接触反応させて炭化水素ガスの燃焼と改質とを行い、この改質器の下流側に設けられた改質ガス路において改質ガスと原料ガスとの熱交換を行って改質器に導入する原料ガスを加熱する。このように、改質に必要な熱エネルギーをバーナー等によって外部から供給するのではなく、燃焼と改質を行って得られた改質ガスの熱によって改質器に導入する原料ガスを加熱するため、極めてエネルギー効率がよくなる。また、改質器周囲にバーナーを備えた加熱炉を設ける必要がなくなり、改質器自体の構造が単純化するとともに、耐熱性や耐圧性を持たせる構造も単純化するため、設備コストも節減できる。
また、上記改質ガス路における水加熱用熱交換器および炭化水素系ガス加熱用熱交換器の上流側に、改質ガスとの熱交換により、上記炭化水素系ガス加熱用熱交換器で加熱された炭化水素系ガスと水加熱用熱交換器で加熱された水から得られた水蒸気との混合ガスである原料ガスを加熱する原料ガス加熱用熱交換器が設けられていることから、加熱するために比較的大きな熱エネルギーを要する炭化水素ガスと水蒸気を原料ガス加熱用熱交換器で加熱してから改質器に導入することから、原料ガスを改質器入口に必要なガス温度に上昇させることができる。
また、改質ガスとの熱交換により、水蒸気源としての水を加熱する水加熱用熱交換器が設けられていることから、原料ガス加熱用熱交換器における原料ガスとの熱交換で、ある程度温度が低下した改質ガスを、さらに水加熱用熱交換器で水と熱交換することにより、さらにエネルギー効率を向上させることができる。
また、改質ガスとの熱交換により、炭化水素系ガスを加熱する炭化水素系ガス加熱用熱交換器が設けられていることから、原料ガス加熱用熱交換器における原料ガスとの熱交換で、ある程度温度が低下した改質ガスを、さらに炭化水素系ガス加熱用熱交換器で炭化水素系ガスと熱交換することにより、さらにエネルギー効率を向上させることができる。
また、原料ガス供給路には、改質器が充分に温度上昇していない水素発生装置の稼動初期において、改質器に導入する原料ガスを加熱する原料ヒータが設けられている。これにより、水素発生装置の稼動初期において、改質器が充分に温度上昇しておらず、熱交換器での原料ガスの加熱が充分行えない段階に、上記原料ヒータによって原料ガスを加熱することができ、装置の稼動初期においても、改質器内の昇温不足から改質反応が低下するのを防止して充分な改質反応を担保できる。
In the reformer, the hydrocarbon gas is contacted with a catalyst together with water vapor and oxygen to cause combustion and reforming of the hydrocarbon gas, and the reformed gas provided on the downstream side of the reformer. The raw material gas introduced into the reformer is heated by exchanging heat between the reformed gas and the raw material gas in the channel. In this way, the raw material gas to be introduced into the reformer is heated by the heat of the reformed gas obtained by combustion and reforming, instead of supplying the heat energy necessary for reforming from the outside by a burner or the like. Therefore, it is extremely energy efficient. In addition, it is no longer necessary to provide a heating furnace with a burner around the reformer, simplifying the structure of the reformer itself, and simplifying the structure to provide heat resistance and pressure resistance, thereby reducing equipment costs. it can.
In addition, heat is exchanged with the reformed gas on the upstream side of the water heating heat exchanger and the hydrocarbon gas heating heat exchanger in the reformed gas path, and the hydrocarbon gas heating heat exchanger is heated. Since a raw material gas heating heat exchanger for heating a raw material gas that is a mixed gas of water vapor obtained from water heated by a heated hydrocarbon gas and water heated by a water heating heat exchanger is provided. Since hydrocarbon gas and water vapor, which require relatively large heat energy, are heated by the heat exchanger for heating the raw material gas and then introduced into the reformer, the raw material gas is brought to the required gas temperature at the reformer inlet. Can be raised.
In addition, since a water heating heat exchanger that heats water as a water vapor source is provided by heat exchange with the reformed gas, heat exchange with the raw material gas in the raw material gas heating heat exchanger is performed to some extent. Energy efficiency can be further improved by heat-exchanging the reformed gas whose temperature has decreased with water using a water heating heat exchanger.
In addition, since a hydrocarbon gas heating heat exchanger that heats the hydrocarbon gas by heat exchange with the reformed gas is provided, heat exchange with the raw material gas in the raw material gas heating heat exchanger is possible. The energy efficiency can be further improved by exchanging the reformed gas whose temperature has decreased to some extent with the hydrocarbon-based gas in the hydrocarbon-gas heating heat exchanger.
The raw material gas supply path is provided with a raw material heater for heating the raw material gas introduced into the reformer at the initial operation of the hydrogen generator in which the temperature of the reformer has not sufficiently increased. As a result, at the initial stage of operation of the hydrogen generator, the reformer is not sufficiently heated, and the source gas is heated by the source heater at a stage where the source gas cannot be sufficiently heated by the heat exchanger. Even in the initial operation of the apparatus, a sufficient reforming reaction can be secured by preventing the reforming reaction from being lowered due to insufficient temperature rise in the reformer.

本発明において、上記水加熱用熱交換器は、改質ガス路において複数設けるようにすることができる。
In the present invention, a plurality of the water heating heat exchangers may be provided in the reformed gas path.

本発明において、上記炭化水素系ガス加熱用熱交換器は、改質ガス路において複数設けるようにすることができる。
In the present invention, a plurality of the hydrocarbon-based gas heating heat exchangers may be provided in the reformed gas path.

本発明において、上記改質ガス中の不純分を吸着する吸着装置を備え、上記吸着装置が加圧真空圧力スイング吸着装置である場合には、加圧真空圧力スイング吸着装置は加圧状態で改質ガス中の不純物を吸着し、真空状態で吸着した不純物の脱着を行うことから、脱着を大気圧で行う加圧圧力スイング式の吸着装置に比べ、脱着後に吸着材に残存する不純物が著しく少なくなる。このため、脱着終了後の製品水素ガスパージにおいてパージガス量を大幅に減らすことができ、パージガスをオフガスとして排出する量を減らすことができる。また、真空状態で脱着を行うことから、吸着材への不純物の吸着量も増え、その分吸着材の充填量を減少させることができる結果、さらにパージガス量を減らし、オフガス量を減らすことが可能になる。さらに、吸着材の充填量を減らさない場合、1回の吸着での不純物の吸着量を増やすことができる結果、圧力スイングの周期を延ばし、時間あたりのパージ回数を減少させることにより、オフガス量を減少させることもできる。本発明ではオフガスを燃焼処理しうる改質器加熱用のバーナーを備えていないことから、オフガス量を減らすことにより処理効率を向上させる効果が極めて顕著である。   In the present invention, when an adsorption device for adsorbing impurities in the reformed gas is provided and the adsorption device is a pressurized vacuum pressure swing adsorption device, the pressurized vacuum pressure swing adsorption device is modified in a pressurized state. Since the impurities in the gas are adsorbed and the impurities adsorbed in a vacuum state are desorbed, the amount of impurities remaining in the adsorbent after desorption is significantly less than the pressure-pressure swing type adsorption device that desorbs at atmospheric pressure. Become. For this reason, the purge gas amount can be significantly reduced in the product hydrogen gas purge after the desorption is completed, and the amount of purge gas discharged as off-gas can be reduced. In addition, since desorption is performed in a vacuum state, the adsorption amount of impurities to the adsorbent also increases, and as a result, the amount of adsorbent filling can be reduced. As a result, the purge gas amount can be further reduced and the off gas amount can be reduced. become. Furthermore, if the amount of adsorbent filling is not reduced, the amount of impurities adsorbed in one adsorption can be increased. As a result, the pressure swing period is extended and the number of purges per hour is reduced, thereby reducing the amount of off-gas. It can also be reduced. In the present invention, since there is no reformer heating burner capable of burning off gas, the effect of improving the treatment efficiency by reducing the amount of off gas is very remarkable.

本発明において、上記改質器では、Rh修飾(Ni−CeO)−Pt触媒を使用することにより、炭化水素の燃焼反応と改質反応とを同じ反応領域内で同時に行なうようになっている場合には、発熱反応である燃焼反応と吸熱反応である改質反応を同じ反応領域内で同時に行うことにより、燃焼反応で発生した熱エネルギーを改質反応の熱源として利用できることから、極めてエネルギー効率がよくなる。さらに、当該反応領域では発熱反応と吸熱反応とが同時に生じることから熱的な中和が起こり、例えば、改質器内に触媒燃焼反応を単独で行う領域を設ける場合に比べ、反応領域の温度上昇がかなり抑制され、改質器に用いる耐熱材料の選定や改質器自体の耐熱構造をそれほど高温仕様のものにしなくてもよくなることから、設備コストも節減できる。 In the present invention, the reformer uses a Rh-modified (Ni—CeO 2 ) —Pt catalyst so that the hydrocarbon combustion reaction and the reforming reaction are simultaneously performed in the same reaction region. In some cases, the combustion reaction, which is an exothermic reaction, and the reforming reaction, which is an endothermic reaction, are simultaneously performed in the same reaction region, so that the heat energy generated in the combustion reaction can be used as a heat source for the reforming reaction. Will be better. Furthermore, since the exothermic reaction and the endothermic reaction occur simultaneously in the reaction region, thermal neutralization occurs. For example, the temperature of the reaction region is higher than that in the case where a region for performing the catalytic combustion reaction alone is provided in the reformer. The rise is considerably suppressed, and it is not necessary to select a heat-resistant material used for the reformer and the heat-resistant structure of the reformer itself to have a high temperature specification, so that the equipment cost can be reduced.

つぎに、本発明を実施するための最良の形態を説明する。   Next, the best mode for carrying out the present invention will be described.

図1は、本発明が適用される水素発生装置の一例を示す構成図である。   FIG. 1 is a configuration diagram showing an example of a hydrogen generator to which the present invention is applied.

この水素発生装置は、炭化水素系ガスを改質して水素リッチな改質ガスを生成する水素発生装置である。上記原料ガスは、一般にプロパンガスや都市ガスのような社会インフラとして供給されている炭化水素系ガスをはじめとして、天然ガス,メタン等の炭化水素系ガスを使用することができる。以下の説明では、炭化水素系ガスとして天然ガスを使用した例を説明する。   This hydrogen generator is a hydrogen generator that reforms a hydrocarbon-based gas to generate a hydrogen-rich reformed gas. The source gas may be a hydrocarbon gas such as natural gas or methane, as well as a hydrocarbon gas generally supplied as social infrastructure such as propane gas or city gas. In the following description, an example in which natural gas is used as the hydrocarbon-based gas will be described.

この水素発生装置は、天然ガスと水蒸気と酸素を原料ガスとして導入して天然ガスの改質を行う改質器1と、上記改質器1から排出された改質ガスをCO変成するCO変成器4と、CO変成された改質ガス中の不純分を吸着する吸着装置5とを備えている。   The hydrogen generator includes a reformer 1 that reforms natural gas by introducing natural gas, water vapor, and oxygen as raw material gases, and a CO shift that converts the reformed gas discharged from the reformer 1 to CO. And an adsorption device 5 for adsorbing impurities in the reformed gas that has been CO-transformed.

また、上記水素発生装置は、上記改質器1に供給する天然ガスを流通させる天然ガス供給路22と、改質器1に導入する水蒸気を発生させるための水を供給して流通させる水供給路23と、上記改質器1に酸素を導入する酸素供給路24とを備えている。上記水供給路23には、供給された水を水蒸気にするスチームヒータ6が設けられている。   Further, the hydrogen generator includes a natural gas supply path 22 through which the natural gas supplied to the reformer 1 is circulated, and a water supply through which water for generating water vapor to be introduced into the reformer 1 is supplied and circulated. A passage 23 and an oxygen supply passage 24 for introducing oxygen into the reformer 1 are provided. The water supply path 23 is provided with a steam heater 6 that converts the supplied water into water vapor.

上記スチームヒータ6から水蒸気を供給するスチーム供給路23aと天然ガス供給路22は、原料ガス供給路10に合流しており、この原料ガス供給路10にはさらに酸素供給路24が合流している。そして、上記原料ガス供給路10が改質器1に接続されて、天然ガスと水蒸気と酸素との混合ガスを原料ガスとして改質器1に導入するようになっている。   The steam supply path 23 a for supplying water vapor from the steam heater 6 and the natural gas supply path 22 merge with the raw material gas supply path 10, and an oxygen supply path 24 further merges with the raw material gas supply path 10. . And the said raw material gas supply path 10 is connected to the reformer 1, and introduce | transduces into the reformer 1 the mixed gas of natural gas, water vapor | steam, and oxygen as raw material gas.

上記改質器1で改質された改質ガスは、改質ガス路25を流通してCO変成器4に導入され、上記CO変成器4で変成された改質ガスは、変成ガス路26を流通して吸着装置5に導入されるようになっている。吸着装置5で不純物が吸着除去された水素ガスは、製品ガス路29から所定の水素ガス使用設備に供給されるようになっている。   The reformed gas reformed by the reformer 1 flows through the reformed gas path 25 and is introduced into the CO converter 4, and the reformed gas transformed by the CO converter 4 is converted into the modified gas path 26. Is distributed and introduced into the adsorption device 5. The hydrogen gas from which impurities are adsorbed and removed by the adsorption device 5 is supplied from a product gas passage 29 to a predetermined hydrogen gas use facility.

上記改質器1は、上記天然ガスを酸素および水蒸気とともに改質触媒と接触反応させて天然ガスの燃焼と改質とを行うものである。具体的には、上記改質器1には、Rh修飾(Ni−CeO)−Pt触媒が使用され、この1種類の触媒により、炭化水素の燃焼反応と改質反応とを同じ反応領域内で同時に行なうようになっている。 The reformer 1 causes the natural gas to come into contact with a reforming catalyst together with oxygen and water vapor to burn and reform the natural gas. Specifically, the reformer 1 uses an Rh-modified (Ni—CeO 2 ) —Pt catalyst, and this one type of catalyst allows the hydrocarbon combustion reaction and the reforming reaction to be performed in the same reaction region. At the same time.

上記改質器1は、図2に示すように、内筒34と外側ケース33との二重構造になっており、上記内筒34の内部に改質触媒31が配置され、内筒34内の1つの反応領域で炭化水素の燃焼反応と改質反応とを同じ反応領域内で同時に行なうようになっている。   As shown in FIG. 2, the reformer 1 has a double structure of an inner cylinder 34 and an outer case 33, and a reforming catalyst 31 is disposed inside the inner cylinder 34, The hydrocarbon combustion reaction and the reforming reaction are simultaneously performed in the same reaction region.

このように、発熱反応である燃焼反応と吸熱反応である改質反応を同じ反応領域内で同時に行うことにより、燃焼反応で発生した熱エネルギーを改質反応の熱源として利用できることから、極めてエネルギー効率がよくなる。さらに、当該反応領域では発熱反応と吸熱反応とが同時に生じることから熱的な中和が起こり、例えば、改質器1内に触媒燃焼反応を単独で行う領域を設ける場合に比べ、反応領域の温度上昇がかなり抑制され、改質器1に用いる耐熱材料の選定や改質器1自体の耐熱構造をそれほど高温仕様のものにしなくてもよくなることから、設備コストも節減できる。なお、改質器1の詳細については後述する。   In this way, the combustion reaction, which is an exothermic reaction, and the reforming reaction, which is an endothermic reaction, are simultaneously performed in the same reaction region, so that the heat energy generated by the combustion reaction can be used as a heat source for the reforming reaction, which is extremely energy efficient Will be better. Furthermore, since the exothermic reaction and the endothermic reaction occur simultaneously in the reaction region, thermal neutralization occurs. For example, compared with the case where a region for performing the catalytic combustion reaction alone is provided in the reformer 1, The temperature rise is considerably suppressed, and it is not necessary to select the heat-resistant material used for the reformer 1 and the heat-resistant structure of the reformer 1 itself so as to have a high-temperature specification, so that the equipment cost can be reduced. Details of the reformer 1 will be described later.

上記改質器1の下流側で改質器1とCO変成器4を接続する改質ガス路25には、改質ガスと原料ガス供給路10を流通する原料ガスとの熱交換を行って上記改質器1に導入する原料ガスを加熱する第1熱交換器3が設けられている。この第1熱交換器3は、原料ガスとして天然ガスと水蒸気との混合ガスを加熱する。   In the reformed gas path 25 connecting the reformer 1 and the CO converter 4 on the downstream side of the reformer 1, heat exchange between the reformed gas and the source gas flowing through the source gas supply path 10 is performed. A first heat exchanger 3 for heating the raw material gas introduced into the reformer 1 is provided. The first heat exchanger 3 heats a mixed gas of natural gas and water vapor as a raw material gas.

このように、改質に必要な熱エネルギーをバーナー等によって外部から供給するのではなく、燃焼と改質を行って得られた改質ガスの熱によって改質器1に導入する原料ガスを加熱するため、極めてエネルギー効率がよくなる。また、改質器1周囲にバーナーを備えた加熱炉を設ける必要がなくなり、改質器1自体の構造が単純化するとともに、耐熱性や耐圧性を持たせる構造も単純化するため、設備コストも節減できる。   In this way, the heat energy necessary for reforming is not supplied from the outside by a burner or the like, but the raw material gas introduced into the reformer 1 is heated by the heat of the reformed gas obtained by combustion and reforming. Therefore, energy efficiency is extremely improved. In addition, it is not necessary to provide a heating furnace with a burner around the reformer 1, the structure of the reformer 1 itself is simplified, and the structure for providing heat resistance and pressure resistance is also simplified. Can also save.

また、上記第1熱交換器3では、炭化水素系ガスと水蒸気との混合ガスを加熱するため、加熱するために比較的大きな熱エネルギーを要する炭化水素ガスと水蒸気を第1熱交換器3で加熱してから改質器1に導入することから、原料ガスを改質器1入口に必要なガス温度に上昇させることができる。   Moreover, in the said 1st heat exchanger 3, in order to heat the mixed gas of hydrocarbon type gas and water vapor | steam, the hydrocarbon gas and water vapor | steam which require comparatively big heat energy in order to heat are heated by the 1st heat exchanger 3. Since it introduce | transduces into the reformer 1 after heating, source gas can be raised to gas temperature required for the reformer 1 inlet_port | entrance.

また、上記第1熱交換器3を後述する他の熱交換器よりも最も改質器1に近い上流側に配置している。これにより、改質器1に導入する直前で最も高温に加熱しなければならない原料ガスが、最も上流側の第1熱交換器3で加熱されることから、原料ガスを充分に高温にしてから改質器1に導入することができ、原料ガスを改質器1入口に必要なガス温度に上昇させることができる。   Further, the first heat exchanger 3 is arranged on the upstream side closest to the reformer 1 than other heat exchangers described later. Thereby, the raw material gas that must be heated to the highest temperature immediately before being introduced into the reformer 1 is heated by the first heat exchanger 3 on the most upstream side. It can be introduced into the reformer 1, and the raw material gas can be raised to the gas temperature required at the inlet of the reformer 1.

上記原料ガス供給路10には、改質器1に導入する原料ガスを加熱する原料ヒータ2が設けられている。これにより、水素発生装置の稼動初期において、改質器1が充分に温度上昇しておらず、第1熱交換器3での原料ガスの加熱が充分行えない段階に、上記原料ヒータ2によって原料ガスを加熱することができ、装置の稼動初期においても、改質器1内の昇温不足から改質反応が低下するのを防止して充分な改質反応を担保できる。   The raw material gas supply path 10 is provided with a raw material heater 2 for heating the raw material gas introduced into the reformer 1. Thereby, at the initial stage of operation of the hydrogen generator, the temperature of the reformer 1 is not sufficiently increased, and the raw material heater 2 supplies the raw material gas when the raw material gas cannot be sufficiently heated in the first heat exchanger 3. The gas can be heated, and even in the initial operation of the apparatus, it is possible to prevent the reforming reaction from being lowered due to insufficient temperature rise in the reformer 1 and to ensure a sufficient reforming reaction.

上記改質ガス路25の第1熱交換器3よりも下流側には、天然ガス供給路22を流通する天然ガスと改質ガスとの熱交換を行って天然ガスを加熱する第2熱交換器9が設けられている。このようにすることにより、第1熱交換器3における原料ガスとの熱交換で、ある程度温度が低下した改質ガスの熱を、さらに第2熱交換器9で天然ガスと熱交換することにより、さらにエネルギー効率を向上させることができる。   On the downstream side of the first heat exchanger 3 in the reformed gas path 25, a second heat exchange is performed in which the natural gas flowing through the natural gas supply path 22 and the reformed gas are subjected to heat exchange to heat the natural gas. A vessel 9 is provided. In this way, by heat exchange with the raw material gas in the first heat exchanger 3, the heat of the reformed gas whose temperature has decreased to some extent is further exchanged with natural gas in the second heat exchanger 9. Furthermore, energy efficiency can be improved.

また、上記改質ガス路25の第1熱交換器3よりも下流側で上記第2熱交換器9よりも下流側には、水蒸気となる水供給路23を流通する水と改質ガスとの熱交換を行って上記水を加熱する第3熱交換器11が設けられている。このようにすることにより、第1熱交換器3における原料ガスとの熱交換と、第2熱交換器9による天然ガスとの熱交換で、ある程度温度が低下した改質ガスの熱を、さらに第3熱交換器11で水と熱交換することにより、さらにエネルギー効率を向上させることができる。   Further, on the downstream side of the reformed gas path 25 from the first heat exchanger 3 and downstream of the second heat exchanger 9, the water and the reformed gas flowing through the water supply path 23 serving as water vapor are provided. A third heat exchanger 11 that heats the water by performing heat exchange is provided. By doing so, the heat of the reformed gas whose temperature has been lowered to some extent by heat exchange with the raw material gas in the first heat exchanger 3 and heat exchange with the natural gas by the second heat exchanger 9 is further increased. Energy exchange can be further improved by exchanging heat with water in the third heat exchanger 11.

上記天然ガス供給路22の第2熱交換器9よりも下流側には、第2熱交換器9で加熱された天然ガスをさらに予熱する予熱ヒータ8と、予熱ヒータ8で予熱された天然ガスから硫黄添加物を除去する脱硫器7が設けられている。なお、上記脱硫器7としては、特に限定するものではなく、吸着材に物理吸着するものであってもよいし、水添脱硫を行うものであってもよい。   On the downstream side of the second heat exchanger 9 in the natural gas supply path 22, a preheating heater 8 for further preheating the natural gas heated by the second heat exchanger 9, and a natural gas preheated by the preheating heater 8. A desulfurizer 7 is provided for removing sulfur additives from the reactor. The desulfurizer 7 is not particularly limited, and may be one that physically adsorbs on the adsorbent, or one that performs hydrodesulfurization.

また、上記水供給路23の第3熱交換器11よりも下流側には、上記第3熱交換器11で加熱された水を水蒸気にするスチームヒータ(水蒸気発生装置)6が設けられている。そして、スチームヒータ6から延びるスチーム供給路23aの先端と脱硫器7から延びる天然ガス供給路22の先端とが原料ガス供給路10に合流して第1熱交換器3に接続されている。   Further, a steam heater (steam generator) 6 that converts water heated by the third heat exchanger 11 into steam is provided downstream of the third heat exchanger 11 in the water supply path 23. . The leading end of the steam supply path 23 a extending from the steam heater 6 and the leading end of the natural gas supply path 22 extending from the desulfurizer 7 join the raw material gas supply path 10 and are connected to the first heat exchanger 3.

また、上記水供給路23には、供給された水道水を純水にする純水装置12と、上記純水装置12から排出された純水を圧送する純水ポンプ13とが設けれている。また、上記天然ガス供給路22には、供給元から供給された天然ガスを圧送するための圧縮機19が設けられている。   The water supply path 23 is provided with a pure water device 12 that makes the supplied tap water pure water, and a pure water pump 13 that pumps pure water discharged from the pure water device 12. . The natural gas supply path 22 is provided with a compressor 19 for pumping the natural gas supplied from the supply source.

さらに、上記CO変成器4から排出された改質ガスを流通させる変成ガス路26には、純水ポンプ13で圧送されて水供給路23を流通する水と、変成ガス路26を流通する改質ガスとの間で熱交換を行って上記水を加熱する第4熱交換器14および第5熱交換器15が設けられている。   Further, the reformed gas passage 26 through which the reformed gas discharged from the CO transformer 4 circulates is supplied by the pure water pump 13 and circulated through the water supply passage 23, and the modified gas passage 26 circulates through the modified gas passage 26. The 4th heat exchanger 14 and the 5th heat exchanger 15 which heat-exchange with quality gas and heat the said water are provided.

上記水供給路23には、第5熱交換器15の下流側で第4熱交換器14の上流側に、純水を加熱する純水ヒータ16が設けられている。そして、純水ポンプ13で送り込まれた水は、第5熱交換器15、純水ヒータ16、第4熱交換器14で予熱されたのち、上記第3熱交換器11に導入されるようになっている。   The water supply path 23 is provided with a pure water heater 16 for heating pure water on the downstream side of the fifth heat exchanger 15 and the upstream side of the fourth heat exchanger 14. The water fed by the pure water pump 13 is preheated by the fifth heat exchanger 15, the pure water heater 16, and the fourth heat exchanger 14, and then introduced into the third heat exchanger 11. It has become.

また、上記変成ガス路26には、上記第4熱交換器14、第5熱交換器15よりもさらに下流側に、圧縮機19で圧縮されて送られる天然ガスと、変成ガス路26を流通する改質ガスとの間で熱交換を行って上記天然ガスを加熱する第6熱交換器17が設けられている。そして、圧縮機19で送り込まれた天然ガスは、第6熱交換器17で予熱されたのち、上記第2熱交換器9に導入されるようになっている。   Further, the natural gas that is compressed by the compressor 19 and sent to the downstream side of the fourth heat exchanger 14 and the fifth heat exchanger 15 and the modified gas passage 26 are circulated in the modified gas passage 26. A sixth heat exchanger 17 is provided that heat-exchanges with the reformed gas to heat the natural gas. The natural gas sent in by the compressor 19 is preheated by the sixth heat exchanger 17 and then introduced into the second heat exchanger 9.

このように、CO変成器4から排出される改質ガスの熱を利用して供給された水および天然ガスを予熱するようになっていることから、さらに熱効率がよくなる。   Thus, since the water and natural gas supplied using the heat of the reformed gas discharged from the CO converter 4 are preheated, the thermal efficiency is further improved.

上記変成ガス路26の上記第6熱交換器17よりもさらに下流側には、改質ガス中に残留した水蒸気を分離除去する気液分離器18が設けられている。気液分離器18で分離除去された水は排水路27から排水される。   A gas-liquid separator 18 that separates and removes water vapor remaining in the reformed gas is provided further downstream of the sixth heat exchanger 17 in the modified gas path 26. The water separated and removed by the gas-liquid separator 18 is drained from the drainage channel 27.

上記気液分離器18の下流側には、上記改質ガス中の不純分であるCOやCOを吸着する吸着装置5が設けられている。 On the downstream side of the gas-liquid separator 18, an adsorption device 5 that adsorbs CO and CO 2 that are impure components in the reformed gas is provided.

上記吸着装置は、それぞれ吸着材が充填された第1吸着塔20aと第2吸着塔20bが並列に存在する圧力スイング式の吸着装置で、一方の吸着塔を高気圧状態にして改質ガスを流通させて吸着材に不純分を吸着させている間、他方の吸着塔を真空ポンプ21で真空引きすることにより吸着材に吸着された不純ガスを脱着する真空脱着を行う加圧真空圧力スイング式の吸着装置である。なお、図示した例は吸着塔が2つのものであるが、吸着塔は3つ以上であってもよい。   The adsorption apparatus is a pressure swing type adsorption apparatus in which a first adsorption tower 20a and a second adsorption tower 20b each filled with an adsorbent are present in parallel, and one of the adsorption towers is in a high-pressure state and the reformed gas is circulated. While the impurity is adsorbed on the adsorbent, the other adsorption tower is evacuated by the vacuum pump 21 to desorb the impurity gas adsorbed on the adsorbent, thereby performing vacuum desorption. Adsorption device. Although the illustrated example has two adsorption towers, the number of adsorption towers may be three or more.

このように、加圧真空圧力スイング式の吸着装置5は、加圧状態で改質ガス中の不純物を吸着し、真空状態で吸着した不純物の脱着を行うことから、脱着を大気圧で行う加圧圧力スイング式の吸着装置に比べ、脱着後に吸着材に残存する不純物が著しく少なくなる。このため、脱着終了後の製品水素ガスパージにおいてパージガス量を大幅に減らすことができ、パージガスをオフガスとして排出する量を減らすことができる。また、真空状態で脱着を行うことから、吸着材への不純物の吸着量も増え、その分吸着材の充填量を減少させることができる結果、さらにパージガス量を減らし、オフガス量を減らすことが可能になる。さらに、吸着材の充填量を減らさない場合、1回の吸着での不純物の吸着量を増やすことができる結果、圧力スイングの周期を延ばし、時間あたりのパージ回数を減少させることにより、オフガス量を減少させることもできる。本発明ではオフガスを燃焼処理しうる改質器加熱用のバーナーを備えていないことから、オフガス量を減らすことにより処理効率を向上させる効果が極めて顕著である。   Thus, the pressurized vacuum pressure swing type adsorption device 5 adsorbs impurities in the reformed gas in a pressurized state and desorbs the impurities adsorbed in a vacuum state, so that the desorption is performed at atmospheric pressure. Compared with the pressure-and-pressure swing type adsorption apparatus, impurities remaining in the adsorbent after desorption are remarkably reduced. For this reason, the purge gas amount can be significantly reduced in the product hydrogen gas purge after the desorption is completed, and the amount of purge gas discharged as off-gas can be reduced. In addition, since desorption is performed in a vacuum state, the adsorption amount of impurities to the adsorbent also increases, and as a result, the amount of adsorbent filling can be reduced. As a result, the purge gas amount can be further reduced and the off gas amount can be reduced. become. Furthermore, if the amount of adsorbent filling is not reduced, the amount of impurities adsorbed in one adsorption can be increased. As a result, the pressure swing period is extended and the number of purges per hour is reduced, thereby reducing the amount of off-gas. It can also be reduced. In the present invention, since there is no reformer heating burner capable of burning off gas, the effect of improving the treatment efficiency by reducing the amount of off gas is very remarkable.

ここで、上記改質器1について詳しく説明する。   Here, the reformer 1 will be described in detail.

上記改質器1は、図2に示すように、上流端から導入された原料ガスを改質して下流端に改質ガスを排出する内筒34と、上記内筒34と所定の断熱空間37を隔てた状態で内筒34を収容する外側ケース33とを備え、内筒34と外側ケース33との二重構造になっており、上記内筒34の内部に改質触媒31が配置されている。なお、図示の上側が上流側であり、下側が下流側である。   As shown in FIG. 2, the reformer 1 includes an inner cylinder 34 that reforms the raw material gas introduced from the upstream end and discharges the reformed gas to the downstream end, and the inner cylinder 34 and a predetermined heat insulating space. And an outer case 33 that accommodates the inner cylinder 34 in a state where the inner cylinder 34 is separated, and has a double structure of the inner cylinder 34 and the outer case 33, and the reforming catalyst 31 is disposed inside the inner cylinder 34. ing. The upper side in the figure is the upstream side, and the lower side is the downstream side.

上記外側ケース33は、有底円筒状で上端部の周縁には盤状のフランジ36aが張り出し形成されている。また、上記フランジ36aの上側には、同じく盤状のフランジ36bが配置され、このフランジ36bには、筒状の導入筒35が外側ケースと略同心となるように配置されている。   The outer case 33 has a bottomed cylindrical shape, and a disk-like flange 36a is formed on the periphery of the upper end portion. Similarly, a plate-like flange 36b is disposed above the flange 36a, and a cylindrical introduction tube 35 is disposed on the flange 36b so as to be substantially concentric with the outer case.

上記導入筒35は、外側ケース33よりも小径で内部に収容された内筒34と略同じ径に設定されており、フランジ36bに接合されて固定され、フランジ36bよりも上流側に突出している。上記導入筒35の上流側の端部開口はフランジ36cで蓋されており、このフランジ36cに原料ガス供給路10が接続され、導入筒35の内部空間に天然ガスと水蒸気と酸素の混合ガスである原料ガスが供給されるようになっている。   The introduction cylinder 35 has a smaller diameter than the outer case 33 and is set to be substantially the same diameter as the inner cylinder 34 accommodated therein. The introduction cylinder 35 is joined and fixed to the flange 36b and protrudes upstream of the flange 36b. . The upstream end opening of the introduction cylinder 35 is covered with a flange 36c. The raw material gas supply path 10 is connected to the flange 36c, and a mixed gas of natural gas, water vapor and oxygen is introduced into the internal space of the introduction cylinder 35. A certain raw material gas is supplied.

一方、上記外側ケースの底部には、改質ガスを流通させる改質ガス路25が接続されており、この改質ガス路25に、第1熱交換器3、第2熱交換器9が設けられている(第3熱交換器11は図示していない)。   On the other hand, a reformed gas path 25 for circulating reformed gas is connected to the bottom of the outer case, and the first heat exchanger 3 and the second heat exchanger 9 are provided in the reformed gas path 25. (The third heat exchanger 11 is not shown).

さらに、上記外側ケースの底部には、内筒34が嵌挿する支受筒38が内部方向に向かって突出するように設けられている。この支受筒38の上部には、多数の流通孔32aが穿設されて触媒31が載置される触媒座32が設けられている。   Further, a support cylinder 38 into which the inner cylinder 34 is fitted is provided at the bottom of the outer case so as to protrude inward. A catalyst seat 32 on which a large number of flow holes 32 a are formed and the catalyst 31 is placed is provided at the upper portion of the support cylinder 38.

そして、上記内筒34は、原料ガスの上流端において外側ケース33に対して固定されている。すなわち、内筒34の上流側の端部は、導入筒35の下流端に溶接されて接合され固定されている。この状態で、上記触媒座32上に触媒31が載置され、内筒34の上記固定端と反対側の下流端が支受筒38に外嵌するように嵌挿されている。   The inner cylinder 34 is fixed to the outer case 33 at the upstream end of the source gas. That is, the upstream end portion of the inner cylinder 34 is welded and joined to the downstream end of the introduction cylinder 35 to be fixed. In this state, the catalyst 31 is placed on the catalyst seat 32, and the downstream end on the opposite side of the fixed end of the inner cylinder 34 is fitted into the support cylinder 38.

この状態で上記内筒34と触媒座32および支受筒38とは固定されておらず、内筒34は触媒座32および支受筒38に対して摺動しうるようになっている。さらに、内筒34の固定端と反対側の下流端は外側ケース33との間に所定隙間40を有して外側ケース33に固定されていない。   In this state, the inner cylinder 34, the catalyst seat 32, and the support cylinder 38 are not fixed, and the inner cylinder 34 can slide relative to the catalyst seat 32 and the support cylinder 38. Further, the downstream end opposite to the fixed end of the inner cylinder 34 is not fixed to the outer case 33 with a predetermined gap 40 between the outer case 33 and the downstream end.

また、上記内筒34と外側ケース33との間の断熱空間37には、図示しない断熱材が充填されている。   Further, the heat insulating space 37 between the inner cylinder 34 and the outer case 33 is filled with a heat insulating material (not shown).

上記外側ケース33、導入筒35、フランジ36a,36b,36cは、耐圧構造を持たせるために所定の圧力に耐えられる厚みを有したステンレス材から構成されている。一方、内筒34には、改質反応の高温に耐えるようインコネル等の耐熱合金が用いられる。このとき、外側ケース33が耐圧構造であるため、内筒34は耐圧設計をする必要がないことから、外側ケース33等を構成する部材より薄い板圧に設定される。   The outer case 33, the introduction cylinder 35, and the flanges 36a, 36b, 36c are made of a stainless material having a thickness capable of withstanding a predetermined pressure in order to provide a pressure resistant structure. On the other hand, a heat resistant alloy such as Inconel is used for the inner cylinder 34 so as to withstand the high temperature of the reforming reaction. At this time, since the outer case 33 has a pressure-resistant structure, the inner cylinder 34 does not need to be pressure-resistant designed. Therefore, the plate pressure is set to be thinner than the members constituting the outer case 33 and the like.

このような構造により、上記改質器1では、原料ガス供給路10から供給された原料ガスを内筒34内で触媒31と接触させて改質し、得られた改質ガスを内筒34から流通孔32a、支受筒38を通過させて改質ガス路25に送るようになっている。   With such a structure, in the reformer 1, the raw material gas supplied from the raw material gas supply path 10 is reformed by bringing the raw material gas into contact with the catalyst 31 in the inner cylinder 34, and the resulting reformed gas is converted into the inner cylinder 34. The flow holes 32 a and the support cylinders 38 are passed through the reformed gas passage 25.

上記触媒31としては、Rh修飾(Ni−CeO)−Pt触媒が使用され、この1種類の触媒により、炭化水素の燃焼反応と改質反応とを、内筒34内の1つの反応領域で炭化水素の燃焼反応と改質反応とを同じ反応領域内で同時に行なうようになっている。 As the catalyst 31, an Rh-modified (Ni—CeO 2 ) —Pt catalyst is used. With this one type of catalyst, a hydrocarbon combustion reaction and a reforming reaction are performed in one reaction region in the inner cylinder 34. The hydrocarbon combustion reaction and the reforming reaction are simultaneously performed in the same reaction region.

上記改質器1は、内部に触媒が配置されて上流端から導入された原料ガスを改質して下流端に改質ガスを排出する内筒34と、上記内筒34と所定の断熱空間37を隔てた状態で内筒34を収容する外側ケース33とを備えているため、改質ガスが流通して内筒34の内部が高温になったとしても、断熱空間37を介して外側ケース33が存在するため、内筒34に比べて外側ケース33はそれほど高温にならない。したがって、内筒34にだけ高温耐久性のある材料を使用し、外側ケース33にはステンレス等の比較的安価な材料を使用することが可能となり、設備コストを大幅に抑えることが可能となる。また、外側ケース33を耐圧構造とすることにより内筒34の耐圧性を考慮する必要がなくなるため、比較的高価な高温耐久材料から形成される内筒34の肉厚を低減することが可能となるため、設備コストを一層抑えることが可能となる。   The reformer 1 includes an inner cylinder 34 that has a catalyst disposed therein, reforms the raw material gas introduced from the upstream end, and discharges the reformed gas to the downstream end, and the inner cylinder 34 and a predetermined heat insulating space. And the outer case 33 that accommodates the inner cylinder 34 in a state where the inner cylinder 34 is separated, even if the reformed gas flows and the inside of the inner cylinder 34 becomes hot, the outer case 33 is interposed via the heat insulating space 37. Since 33 exists, the outer case 33 does not become so hot as compared with the inner cylinder 34. Therefore, it is possible to use a material having a high temperature durability only for the inner cylinder 34 and to use a relatively inexpensive material such as stainless steel for the outer case 33, so that the equipment cost can be greatly reduced. In addition, since the outer case 33 has a pressure-resistant structure, it is not necessary to consider the pressure resistance of the inner cylinder 34, so that the thickness of the inner cylinder 34 formed from a relatively expensive high-temperature durable material can be reduced. Therefore, the facility cost can be further reduced.

さらに、上記内筒34は、原料ガスの上流端において外側ケース33に対して固定され、その固定端と反対側の端部は外側ケース33との間に所定隙間40を有して外側ケース33に固定されていないため、内筒34が高温になって熱膨張し、温度上昇が抑えられた外側ケース33との間で大きく熱膨張の差が生じたとしても、内筒34と外側ケース33の熱膨張差は、外側ケース33と内筒34との間の上記所定隙間40で吸収される。したがって、高温になる内筒34と比較的低温の外側ケース33との間の応力集中が生じることがなく、従来問題となっていたような起動停止の繰り返しでクリープ疲労破壊を生じるようなことがなくなる。   Further, the inner cylinder 34 is fixed to the outer case 33 at the upstream end of the source gas, and the outer case 33 has a predetermined gap 40 between the end opposite to the fixed end and the outer case 33. Therefore, even if a large difference in thermal expansion occurs between the inner case 34 and the outer case 33 in which the temperature rise is suppressed, the inner case 34 and the outer case 33 are heated. Is absorbed by the predetermined gap 40 between the outer case 33 and the inner cylinder 34. Accordingly, there is no concentration of stress between the inner tube 34 that is at a high temperature and the outer case 33 that is at a relatively low temperature, and creep fatigue failure is caused by repeated start and stop, which has been a problem in the past. Disappear.

また、上記改質器1では、上記内筒34の固定端が上流端であるため、内筒34の固定端における接合部の損傷を未然に防止できる。すなわち、外側ケース33に対して固定された内筒34の固定端と反対側の端部が上流端であると、原料ガスが流れたときに当該端部と外側ケース33との間の所定隙間40の部分で原料ガスの流れが乱れて、内筒34自体に振動は発生し、固定端に応力が加わってその接合部が損傷しやすいが、上記固定端を上流端として上記所定隙間40を下流側に配置することにより、原料ガスの流れをスムーズにして内筒34の振動を防止し、固定端に加わる応力を大幅に低減してその接合部の損傷が防止される。   Further, in the reformer 1, since the fixed end of the inner cylinder 34 is the upstream end, damage to the joint portion at the fixed end of the inner cylinder 34 can be prevented in advance. That is, when the end opposite to the fixed end of the inner cylinder 34 fixed to the outer case 33 is the upstream end, a predetermined gap between the end and the outer case 33 when the source gas flows. The flow of the raw material gas is disturbed in the portion 40, and vibration is generated in the inner cylinder 34 itself, and stress is applied to the fixed end and the joint is easily damaged. However, the predetermined gap 40 is formed with the fixed end as an upstream end. By disposing on the downstream side, the flow of the raw material gas is made smooth to prevent the vibration of the inner cylinder 34, the stress applied to the fixed end is greatly reduced, and the joint portion is prevented from being damaged.

さらに、上記改質器1では、上記外側ケース33に設けられた支受筒38が、上記内筒34の固定端と反対側の端部において内筒34と嵌挿して内筒34の当該端部のずれを防止するずれ防止部材として機能する。このため、内筒34の固定端における接合部の損傷を未然に防止できる。すなわち、外側ケース33に対して固定された内筒34の固定端と反対側の端部が自由端になっていると、改質器1自体に外力が加わったような場合に内筒34自体が振動し、固定端に大きな応力が加わり、その接合部が損傷しやすいが、当該固定端と反対側の端部に嵌挿する支受筒38(ずれ防止部材)を設けることにより、改質器1に外力が加わったとしても、内筒34の振動が防止され、固定端に加わる応力を大幅に低減し、その接合部の損傷を防止できる。   Further, in the reformer 1, the support cylinder 38 provided in the outer case 33 is fitted and inserted into the inner cylinder 34 at the end opposite to the fixed end of the inner cylinder 34. It functions as a displacement prevention member that prevents displacement of the portion. For this reason, damage to the joint portion at the fixed end of the inner cylinder 34 can be prevented in advance. That is, when the end opposite to the fixed end of the inner cylinder 34 fixed to the outer case 33 is a free end, the inner cylinder 34 itself is applied when an external force is applied to the reformer 1 itself. Vibrates, a large stress is applied to the fixed end, and the joint is easily damaged. However, by providing a support tube 38 (displacement prevention member) that is fitted into the end opposite to the fixed end, the modification is improved. Even if an external force is applied to the vessel 1, the vibration of the inner cylinder 34 is prevented, the stress applied to the fixed end is greatly reduced, and damage to the joint can be prevented.

なお、上述した例では、上記内筒34の固定端が上流端とした場合を説明したが、上記内筒34は、原料ガスの上流端と下流端のうちいずれか一端側において外側ケース33に対して固定されていれば、本発明に含む趣旨である。   In the above-described example, the case where the fixed end of the inner cylinder 34 is the upstream end has been described. However, the inner cylinder 34 is connected to the outer case 33 at either one of the upstream end and the downstream end of the source gas. If it is fixed with respect to it, it is the meaning included in this invention.

図3は、本発明が適用される改質器1の第2例である。この例では、内筒34の内部に溶接で触媒座32が固定されて触媒31が載置されている。また、外側ケース33が筒状に形成され、内筒34の下流端が第1熱交換器3内に大きく開口している。そして、外側ケース33の下流端寄りの部分には、内向きに突出する盤状部材39が取り付けられており、この盤状部材39がずれ防止部材として機能している。それ以外は上記第1例と同様であり、同様の部分には同じ符号を付している。   FIG. 3 shows a second example of the reformer 1 to which the present invention is applied. In this example, the catalyst seat 32 is fixed to the inside of the inner cylinder 34 by welding, and the catalyst 31 is placed. Further, the outer case 33 is formed in a cylindrical shape, and the downstream end of the inner cylinder 34 is greatly opened in the first heat exchanger 3. A disc-like member 39 that protrudes inward is attached to a portion near the downstream end of the outer case 33, and this disc-like member 39 functions as a displacement prevention member. Other than that, it is the same as that of the said 1st example, and attaches | subjects the same code | symbol to the same part.

上記水素発生装置により、例えば、つぎのようにして水素の発生が行われる。   For example, hydrogen is generated by the hydrogen generator as follows.

すなわち、原料として供給された天然ガスは、圧縮機19で圧縮されて天然ガス供給路22を流通する過程で、第6熱交換器17で変成ガス路26を流通する改質ガスと熱交換されて加熱され、第2熱交換器9で改質ガス路25を流通する改質ガスと熱交換されて加熱される。さらに、予熱ヒータ8で加熱されて脱硫器7で硫黄添加物が除去されて原料ガス供給路10に導入される。   That is, the natural gas supplied as a raw material is heat-exchanged with the reformed gas flowing through the modified gas path 26 by the sixth heat exchanger 17 in the process of being compressed by the compressor 19 and flowing through the natural gas supply path 22. The second heat exchanger 9 exchanges heat with the reformed gas flowing through the reformed gas path 25 and is heated. Further, it is heated by the preheating heater 8 and the sulfur additive is removed by the desulfurizer 7 and introduced into the raw material gas supply path 10.

一方、原料として供給された水道水は、純水装置12で純水にしてから純水ポンプ13で圧送されて水供給路23を流通する。その過程で、第5熱交換器15、第4熱交換器14で変成ガス路26を流通する改質ガスと熱交換されて加熱されるとともに、純水ヒータ16でも加熱される、さらに、第3熱交換器11で改質ガス路25を流通する改質ガスと熱交換されて加熱され、スチームヒータ6でスチーム化されてスチーム供給路23aを経て原料ガス供給路10に導入される。   On the other hand, tap water supplied as a raw material is made pure water by the pure water device 12 and then pumped by the pure water pump 13 to circulate through the water supply path 23. In the process, the fifth heat exchanger 15 and the fourth heat exchanger 14 are heated by being exchanged with the reformed gas flowing through the shift gas passage 26 and heated by the pure water heater 16. The heat is exchanged with the reformed gas flowing through the reformed gas path 25 in the three heat exchanger 11 and heated, steamed by the steam heater 6, and introduced into the raw material gas supply path 10 through the steam supply path 23a.

原料ガス供給路10に導入された天然ガスと水蒸気は、原料ガス路を流通する間に混合ガスとなり、第1熱交換器3で改質ガス路25を流通する改質ガスと熱交換されて加熱される。この原料ガス供給路10には、さらに酸素供給路24に供給された酸素が導入され、天然ガスと水蒸気と酸素の混合ガスが原料ガスとして改質器1に供給される。   The natural gas and water vapor introduced into the source gas supply path 10 become a mixed gas while flowing through the source gas path, and are heat-exchanged with the reformed gas flowing through the reformed gas path 25 in the first heat exchanger 3. Heated. Oxygen supplied to the oxygen supply path 24 is further introduced into the source gas supply path 10, and a mixed gas of natural gas, water vapor, and oxygen is supplied to the reformer 1 as a source gas.

改質器1では、Rh修飾(Ni−CeO)−Pt触媒により、炭化水素の燃焼反応と改質反応とを、内筒34内の1つの反応領域で炭化水素の燃焼反応と改質反応とが同じ反応領域内で同時に行なわれる。 In the reformer 1, the hydrocarbon combustion reaction and the reforming reaction are performed by the Rh-modified (Ni—CeO 2 ) -Pt catalyst, and the hydrocarbon combustion reaction and the reforming reaction are performed in one reaction region in the inner cylinder 34. Are performed simultaneously in the same reaction zone.

すなわち、炭化水素の一部を完全燃焼させて炭化水素をCOとHOとに変換させる燃焼反応と、この燃焼反応により生成したCOおよびHOのそれぞれをさらに残余の炭化水素と反応させてHとCOとに変換させる改質反応とを、前記触媒上で進行させ、炭化水素をHとCOとに変換させるのである。 That is, a combustion reaction in which part of the hydrocarbon is completely burned to convert the hydrocarbon into CO and H 2 O, and each of CO 2 and H 2 O generated by this combustion reaction is further reacted with the remaining hydrocarbon. the reforming reaction and for converting by the H 2 and CO, is allowed to proceed over the catalyst, it is of to convert hydrocarbons to H 2 and CO.

例えば、炭化水素がメタンの場合を例にあげて説明すると、その反応は全体として下記の式(1)のように表わされるが、実際は(2)〜(4)式のように、燃焼反応で生成したCOとHOがさらにCHと改質反応を起こしてCOとHに変換するという逐次反応となっている。
CH+2O→4CO+8H (1)
CH+2O→CO+2HO (2)
CH+CO→2CO+2H (3)
2CH+2HO→2CO+6H (4)
For example, the case where the hydrocarbon is methane will be described as an example, and the reaction is generally expressed as in the following formula (1), but in reality, it is a combustion reaction as expressed in the formulas (2) to (4). This is a sequential reaction in which the produced CO 2 and H 2 O further undergo a reforming reaction with CH 4 and are converted to CO and H 2 .
CH 4 + 2O 2 → 4CO + 8H 2 (1)
CH 4 + 2O 2 → CO 2 + 2H 2 O (2)
CH 4 + CO 2 → 2CO + 2H 2 (3)
2CH 4 + 2H 2 O → 2CO + 6H 2 (4)

上記のCHとOとの接触反応に際しては、さらに系にCOや2HOを供給することもできる。この場合は、COや2HOの供給量に見合ってOの供給量を減ずることができる。 In the contact reaction between CH 4 and O 2 , CO 2 or 2H 2 O can be further supplied to the system. In this case, the supply amount of O 2 can be reduced in accordance with the supply amount of CO 2 or 2H 2 O.

反応温度は350〜800℃、殊に400〜750℃程度が適当である。反応温度はCHとOとの反応によって一部補われるが、不足分は外部加熱することになる。反応温度が余りに低いときはCHの改質反応自体が円滑に進行せず、一方反応温度が余りに高いときは、熱エネルギー的に不利となる上、CHの熱分解によるカーボンの析出が起こる傾向がある。反応圧力は通常は加圧条件が採用されるが、常圧でもよい。 The reaction temperature is suitably from 350 to 800 ° C, particularly from about 400 to 750 ° C. Although the reaction temperature is partially compensated by the reaction of CH 4 and O 2 , the shortage is externally heated. When the reaction temperature is too low, the reforming reaction of CH 4 itself does not proceed smoothly. On the other hand, when the reaction temperature is too high, it is disadvantageous in terms of thermal energy, and carbon deposition occurs due to thermal decomposition of CH 4. Tend. The reaction pressure is usually a pressurizing condition, but may be normal pressure.

この改質工程によって得られる改質ガスの組成は、ドライベースで大略70%H+15%CO+15%CO、残部は不純分である。この改質工程は、触媒上の発熱反応であり、出口部分の改質ガスの温度は、約700〜800℃程度である。 The composition of the reformed gas obtained by this reforming process is approximately 70% H 2 + 15% CO + 15% CO 2 on a dry basis, with the remainder being impure. This reforming process is an exothermic reaction on the catalyst, and the temperature of the reformed gas at the outlet is about 700 to 800 ° C.

上記Rh修飾(Ni-CeO)-Pt触媒は、例えば、適当な空隙率を有するアルミナ担体表面にRhを担持させ、ついでPtを担持させ、さらにNiとCeOとを同時担持させることにより得られる。ただし、担体の材質や形状の選択、被覆物形成の有無またはその材質の選択は、種々のバリエーションが可能である。 The Rh-modified (Ni—CeO 2 ) -Pt catalyst is obtained, for example, by supporting Rh on an alumina support surface having an appropriate porosity, then supporting Pt, and simultaneously supporting Ni and CeO 2. It is done. However, various variations are possible for the selection of the material and shape of the carrier, the presence / absence of coating formation, and the selection of the material.

Rhの担持は、Rhの水溶性塩の水溶液を含浸後、乾燥、焼成、水素還元することにより行われる。また、Ptの担持は、Ptの水溶性塩の水溶液を含浸後、乾燥、焼成、水素還元することにより行われる。NiおよびCeOの同時担持は、Niの水溶性塩およびCeの水溶性塩の混合水溶液を含浸後、乾燥、焼成、水素還元することにより行われる。 Rh is supported by impregnating an aqueous solution of a water-soluble salt of Rh, followed by drying, firing, and hydrogen reduction. Pt is supported by impregnating an aqueous solution of a Pt water-soluble salt, followed by drying, firing, and hydrogen reduction. Simultaneous loading of Ni and CeO 2 is performed by impregnating a mixed aqueous solution of a water-soluble salt of Ni and a water-soluble salt of Ce, followed by drying, firing, and hydrogen reduction.

上に例示した手順により、目的とするRh修飾(Ni−CeO)−Pt触媒が得られる。各成分の組成は重量比で、Rh:Ni:CeO:Pt=(0.05−0.5):(3.0−10.0):(2.0−8.0):(0.3−5.0)、望ましくは、Rh:Ni:CeO:Pt=(0.1−0.4):(4.0−9.0):(2.0−5.0):(0.3−3.0)に設定することが好ましい。 The target Rh-modified (Ni—CeO 2 ) -Pt catalyst is obtained by the procedure exemplified above. The composition of each component is Rh: Ni: CeO 2 : Pt = (0.05-0.5) :( 3.0-10.0) :( 2.0-8.0) :( 0 .3-5.0), preferably Rh: Ni: CeO 2 : Pt = (0.1-0.4) :( 4.0-9.0) :( 2.0-5.0): It is preferable to set to (0.3-3.0).

なお、上記における各段階での水素還元処理を省略し、実際の使用に際して触媒31を高温で水素還元して用いることもできる。各段階で水素還元処理を行ったときも、さらに使用に際して触媒31を高温で水素還元して用いることができる。   In addition, the hydrogen reduction process in each step in the above may be omitted, and the catalyst 31 may be used after being reduced with hydrogen at a high temperature in actual use. Even when the hydrogen reduction treatment is performed at each stage, the catalyst 31 can be further reduced with hydrogen at a high temperature before use.

上記CO変成器4では、改質ガス中のCOをCOに変成するCO変成工程が行なわれる。 In the CO converter 4, a CO conversion process for converting CO in the reformed gas into CO 2 is performed.

すなわち、改質ガスに含まれる約15%のCO中約10数%のCOとスチーム(HO)を下記の反応式のように反応させてCOとHに変成する。このCO変成工程を経ることにより、改質ガスの組成は、ドライベースで大略77%H+22%CO+1%CO+残部不純分となる。
CO+HO→CO+H
That is, about 10 to several tens percent of CO and steam (H 2 O) in about 15% of CO contained in the reformed gas are reacted as shown in the following reaction formula to be converted into CO 2 and H 2 . Through this CO conversion step, the composition of the reformed gas becomes approximately 77% H 2 + 22% CO 2 + 1% CO + remaining impurity content on a dry basis.
CO + H 2 O → CO 2 + H 2

なお、必要に応じて、上記CO変成器4の下流側に、CO変成工程を経て残留したCOを酸化させてCOにするCO選択酸化器を設けてもよい。すなわち、COと空気中のOとを下記の反応式のように反応させてCOにする。このCO選択酸化により、残留するCO分は10ppm以下となり、改質ガスの組成は、大略77%H+23%CO+残部不純分となり、燃料電池等の水素ガス利用設備に対して供給される。
2CO+O→2CO
If necessary, a CO selective oxidizer may be provided on the downstream side of the CO converter 4 to oxidize the CO remaining after the CO conversion step to CO 2 . That is, CO and O 2 in the air are reacted as shown in the following reaction formula to form CO 2 . By this CO selective oxidation, the residual CO content is 10 ppm or less, and the reformed gas composition is approximately 77% H 2 + 23% CO 2 + the remaining impure component, which is supplied to hydrogen gas utilization equipment such as fuel cells. The
2CO + O 2 → 2CO 2

また、上述した例では、改質触媒としてRh修飾(Ni-CeO)-Pt触媒を用いた例を示したが、炭化水素の燃焼反応と改質反応とを同じ反応領域内で同時に行ないうるものであれば、他の触媒を用いることもできる。 In the above-described example, the Rh-modified (Ni—CeO 2 ) —Pt catalyst is used as the reforming catalyst. However, the hydrocarbon combustion reaction and the reforming reaction can be performed simultaneously in the same reaction region. Other catalysts can be used as long as they are suitable.

以上のように、上記水素発生装置および方法は、発熱反応である燃焼反応と吸熱反応である改質反応を同じ反応領域内で同時に行うことにより、燃焼反応で発生した熱エネルギーを改質反応の熱源として利用できることから、極めてエネルギー効率がよくなる。さらに、当該反応領域では発熱反応と吸熱反応とが同時に生じることから熱的な中和が起こり、例えば、改質器1内に触媒燃焼反応を単独で行う領域を設ける場合に比べ、反応領域の温度上昇がかなり抑制され、改質器1に用いる耐熱材料の選定や改質器1自体の耐熱構造をそれほど高温仕様のものにしなくてもよくなることから、設備コストも節減できる。   As described above, the hydrogen generation apparatus and method perform the combustion reaction, which is an exothermic reaction, and the reforming reaction, which is an endothermic reaction, simultaneously in the same reaction region, thereby converting the thermal energy generated in the combustion reaction to the reforming reaction. Since it can be used as a heat source, it is extremely energy efficient. Furthermore, since the exothermic reaction and the endothermic reaction occur simultaneously in the reaction region, thermal neutralization occurs. For example, compared with the case where a region for performing the catalytic combustion reaction alone is provided in the reformer 1, The temperature rise is considerably suppressed, and it is not necessary to select the heat-resistant material used for the reformer 1 and the heat-resistant structure of the reformer 1 itself so as to have a high-temperature specification, so that the equipment cost can be reduced.

また、上記改質器1は、改質ガスが流通して内筒34の内部が高温になったとしても、断熱空間37を介して外側ケース33が存在するため、内筒34に比べて外側ケース33はそれほど高温にならない。したがって、内筒34にだけ高温耐久性のある材料を使用し、外側ケース33にはステンレス等の比較的安価な材料を使用することが可能となり、設備コストを大幅に抑えることが可能となる。また、外側ケース33を耐圧構造とすることにより内筒34の耐圧性を考慮する必要がなくなるため、比較的高価な高温耐久材料から形成される内筒34の肉厚を低減することが可能となるため、設備コストを一層抑えることが可能となる。さらに、内筒34が高温になって熱膨張し、温度上昇が抑えられた外側ケース33との間で大きく熱膨張の差が生じたとしても、内筒34と外側ケース33の熱膨張差は、外側ケース33と内筒34との間の上記所定隙間40で吸収される。したがって、高温になる内筒34と比較的低温の外側ケース33との間の応力集中が生じることがなく、従来問題となっていたような起動停止の繰り返しでクリープ疲労破壊を生じるようなことがなくなる。   In addition, the reformer 1 has an outer case 33 through the heat insulating space 37 even when the reformed gas flows and the inside of the inner cylinder 34 becomes hot. Case 33 does not become so hot. Therefore, it is possible to use a material having a high temperature durability only for the inner cylinder 34 and to use a relatively inexpensive material such as stainless steel for the outer case 33, so that the equipment cost can be greatly reduced. In addition, since the outer case 33 has a pressure-resistant structure, it is not necessary to consider the pressure resistance of the inner cylinder 34, so that the thickness of the inner cylinder 34 formed from a relatively expensive high-temperature durable material can be reduced. Therefore, the facility cost can be further reduced. Furthermore, even if the inner cylinder 34 becomes hot and thermally expands and a large difference in thermal expansion occurs between the outer case 33 and the temperature rise is suppressed, the difference in thermal expansion between the inner cylinder 34 and the outer case 33 is It is absorbed in the predetermined gap 40 between the outer case 33 and the inner cylinder 34. Accordingly, there is no concentration of stress between the inner tube 34 that is at a high temperature and the outer case 33 that is at a relatively low temperature, and creep fatigue failure is caused by repeated start and stop, which has been a problem in the past. Disappear.

図4は、本発明が適用される改質器1の第3例である。この例は、いわゆるオートサーマル方式の改質を行うものであり、上述したRh修飾(Ni−CeO)−Pt触媒等により、炭化水素の燃焼反応と改質反応とを同じ反応領域内で同時に行なうのではなく、触媒として原料ガスの上流側に燃焼触媒41が配置され、その下流側に改質触媒42が配置されている。 FIG. 4 shows a third example of the reformer 1 to which the present invention is applied. In this example, so-called autothermal reforming is performed, and the above-described Rh-modified (Ni—CeO 2 ) —Pt catalyst or the like allows a hydrocarbon combustion reaction and a reforming reaction to be simultaneously performed in the same reaction region. Instead, the combustion catalyst 41 is disposed upstream of the raw material gas as a catalyst, and the reforming catalyst 42 is disposed downstream thereof.

この改質器1では、改質触媒42での改質反応に必要な熱エネルギーは、原料ガスを燃焼触媒41によって燃焼した燃焼エネルギーによって補われるようになっている。   In the reformer 1, the thermal energy necessary for the reforming reaction in the reforming catalyst 42 is supplemented by the combustion energy obtained by burning the raw material gas with the combustion catalyst 41.

原料ガスとして、例えば、メタンを用い、このメタンの一部を量論比以下で燃焼させた場合、燃料ガスは以下の反応となる。   For example, when methane is used as the raw material gas and a part of the methane is burned at a stoichiometric ratio or less, the fuel gas undergoes the following reaction.

CH+1/2O=2H+CO・・・(1)
CH+2O=CO+2HO・・・(2)
このときの反応は発熱反応であり、燃料電池で必要とされる水素が発生するという利点がある。
CH 4 + 1 / 2O 2 = 2H 2 + CO (1)
CH 4 + 2O 2 = CO 2 + 2H 2 O (2)
The reaction at this time is an exothermic reaction and has an advantage that hydrogen required in the fuel cell is generated.

原料ガスの一部が燃焼触媒で部分燃焼されて(1)式および(2)式の反応により水素が発生する過程で、(2)式の反応で発生した蒸気は、残りの原料ガスと反応し、次式の改質反応により、水素が発生する。   In the process where a part of the raw material gas is partially burned by the combustion catalyst and hydrogen is generated by the reaction of the equations (1) and (2), the vapor generated by the reaction of the equation (2) reacts with the remaining raw material gas. However, hydrogen is generated by the reforming reaction of the following formula.

CH+HO=3H+CO・・・(3)
すなわち、改質触媒において蒸気と残りの原料ガスとが反応すると、水素リッチな改質ガスが生成されることになる。
CH 4 + H 2 O = 3H 2 + CO (3)
That is, when the steam and the remaining raw material gas react in the reforming catalyst, a hydrogen-rich reformed gas is generated.

それ以外は、上述した実施例と同様であり同様の作用効果を奏する。   Other than that, it is the same as that of the above-mentioned Example, and there exists the same effect.

本発明は、家庭用燃料電池用の水素発生装置に適用できるだけでなく、自動車用、プラント用その他の燃料電池用の水素発生装置にも適用できるし、燃料電池以外の水素ガス利用設備に対して水素ガスを供給するための水素発生装置にも適用することができる。   The present invention can be applied not only to hydrogen generators for household fuel cells, but also to hydrogen generators for automobiles, plants, and other fuel cells, and for hydrogen gas utilization equipment other than fuel cells. The present invention can also be applied to a hydrogen generator for supplying hydrogen gas.

本発明が適用される水素発生装置の一実施例を示す図である。It is a figure which shows one Example of the hydrogen generator to which this invention is applied. 本発明が適用される改質器の一実施例を示す断面図である。It is sectional drawing which shows one Example of the reformer to which this invention is applied. 上記改質器の第2例を示す断面図である。It is sectional drawing which shows the 2nd example of the said reformer. 上記改質器の第3例を示す断面図である。It is sectional drawing which shows the 3rd example of the said reformer.

符号の説明Explanation of symbols

1 改質器
2 原料ヒータ
3 第1熱交換器
4 CO変成器
5 吸着装置
6 スチームヒータ
7 脱硫器
8 予熱ヒータ
9 第2熱交換器
10 原料ガス供給路
11 第3熱交換器
12 純水装置
13 純水ポンプ
14 第4熱交換器
15 第5熱交換器
16 純水ヒータ
17 第6熱交換器
18 気液分離器
19 圧縮機
20a 第1吸着塔
20b 第2吸着塔
21 真空ポンプ
22 天然ガス供給路
23 水供給路
23a スチーム供給路
24 酸素供給路
25 改質ガス路
26 変成ガス路
27 排水路
29 製品ガス路
31 改質触媒
32 触媒座
32a 流通孔
33 外側ケース
34 内筒
35 導入筒
36a フランジ
36b フランジ
36c フランジ
37 断熱空間
38 支受筒
39 盤状部材
40 所定隙間
41 燃焼触媒
42 改質触媒
DESCRIPTION OF SYMBOLS 1 Reformer 2 Raw material heater 3 1st heat exchanger 4 CO converter 5 Adsorption device 6 Steam heater 7 Desulfurizer 8 Preheating heater 9 2nd heat exchanger 10 Raw material gas supply path 11 3rd heat exchanger 12 Pure water apparatus DESCRIPTION OF SYMBOLS 13 Pure water pump 14 4th heat exchanger 15 5th heat exchanger 16 Pure water heater 17 6th heat exchanger 18 Gas-liquid separator 19 Compressor 20a 1st adsorption tower 20b 2nd adsorption tower 21 Vacuum pump 22 Natural gas Supply path 23 Water supply path 23a Steam supply path 24 Oxygen supply path 25 Reformed gas path 26 Metamorphic gas path 27 Drainage path 29 Product gas path 31 Reformed catalyst 32 Catalyst seat 32a Flow hole 33 Outer case 34 Inner cylinder 35 Introducing cylinder 36a Flange 36b Flange 36c Flange 37 Heat insulation space 38 Bearing cylinder 39 Disc member 40 Predetermined gap 41 Combustion catalyst 42 Reforming catalyst

Claims (5)

炭化水素系ガスを改質して水素リッチな改質ガスを生成する水素発生装置であって、
上記炭化水素系ガスを水蒸気および酸素とともに触媒と接触反応させて炭化水素ガスの燃焼と改質とを行う改質器を備え、
上記改質器の下流側に設けられた改質ガス路には、
改質ガスとの熱交換により、水蒸気源としての水を加熱する水加熱用熱交換器と、
改質ガスとの熱交換により、炭化水素系ガスを加熱する炭化水素系ガス加熱用熱交換器が設けられ、
さらに、上記改質ガス路における水加熱用熱交換器および炭化水素系ガス加熱用熱交換器の上流側に、改質ガスとの熱交換により、上記炭化水素系ガス加熱用熱交換器で加熱された炭化水素系ガスと水加熱用熱交換器で加熱された水から得られた水蒸気との混合ガスである原料ガスを加熱する原料ガス加熱用熱交換器が設けられ、
さらに、上記原料ガスを供給する原料ガス供給路には、改質器が充分に温度上昇していない水素発生装置の稼動初期において、改質器に導入する原料ガスを加熱する原料ヒータが設けられ
上記水加熱用熱交換器、炭化水素系ガス加熱用熱交換器、原料ガス加熱用熱交換器および原料ヒータには酸素ガスを導入せずに、原料ガス供給路に酸素ガスを導入することを特徴とする水素発生装置。
A hydrogen generator for reforming a hydrocarbon gas to produce a hydrogen-rich reformed gas,
Comprising a reformer that causes the hydrocarbon gas to contact and react with the catalyst together with water vapor and oxygen to burn and reform the hydrocarbon gas;
In the reformed gas path provided on the downstream side of the reformer,
A heat exchanger for water heating that heats water as a water vapor source by heat exchange with the reformed gas;
A heat exchanger for heating a hydrocarbon gas that heats the hydrocarbon gas by heat exchange with the reformed gas is provided,
Further, heating with the hydrocarbon gas heating heat exchanger is performed upstream of the water heating heat exchanger and the hydrocarbon gas heating heat exchanger in the reformed gas path by heat exchange with the reformed gas. A raw material gas heating heat exchanger for heating a raw material gas that is a mixed gas of the hydrocarbon-based gas and water vapor obtained from water heated by the water heating heat exchanger,
Further, the raw material gas supply path for supplying the raw material gas is provided with a raw material heater for heating the raw material gas introduced into the reformer in the initial operation of the hydrogen generator in which the temperature of the reformer has not sufficiently increased. ,
The water-heating heat exchanger, hydrocarbon gas heat exchanger for heating, without introducing oxygen gas into the heat exchanger and the raw material for the heater material gas heating, Rukoto to introduce oxygen gas into the raw material gas supply passage A hydrogen generator characterized by
上記水加熱用熱交換器は、改質ガス路において複数設けられている請求項1記載の水素発生装置。   The hydrogen generator according to claim 1, wherein a plurality of the water heating heat exchangers are provided in the reformed gas path. 上記炭化水素系ガス加熱用熱交換器は、改質ガス路において複数設けられている請求項1または2記載の水素発生装置。   The hydrogen generator according to claim 1 or 2, wherein a plurality of the hydrocarbon-based gas heating heat exchangers are provided in the reformed gas path. 上記改質ガス中の不純分を吸着する吸着装置を備え、上記吸着装置が加圧真空圧力スイング吸着装置である請求項1〜のいずれか一項に記載の水素発生装置。 The hydrogen generator according to any one of claims 1 to 4 , further comprising an adsorption device that adsorbs impurities in the reformed gas, wherein the adsorption device is a pressurized vacuum pressure swing adsorption device. 炭化水素系ガスを改質して水素リッチな改質ガスを生成する水素発生方法であって、
上記炭化水素系ガスを水蒸気および酸素とともに触媒と接触反応させて炭化水素ガスの燃焼と改質とを行う改質工程と、
上記改質工程の下流側において、
改質ガスとの熱交換により、水蒸気源としての水を加熱する水加熱用熱交換工程と、
改質ガスとの熱交換により、炭化水素系ガスを加熱する炭化水素系ガス加熱用熱交換工程を行ない、
さらに、上記改質ガス路における水加熱用熱交換工程および炭化水素系ガス加熱用熱交換工程の上流側において、改質ガスとの熱交換により、上記炭化水素系ガス加熱用熱交換工程で加熱された炭化水素系ガスと水加熱用熱交換工程で加熱された水から得られた水蒸気との混合ガスである原料ガスを加熱する原料ガス加熱用熱交換工程を行い、
さらに、上記原料ガスを供給する原料ガス供給段階において、改質器が充分に温度上昇していない水素発生装置の稼動初期において、改質器に導入する原料ガスを加熱する原料加熱工程を行い、
上記水加熱用熱交換工程、炭化水素系ガス加熱用熱交換工程、原料ガス加熱用熱交換工程および原料加熱工程では酸素ガスを導入せずに、上記原料ガス供給段階において酸素ガスを導入することを特徴とする水素発生方法。
A hydrogen generation method for reforming a hydrocarbon gas to produce a hydrogen-rich reformed gas,
A reforming step of bringing the hydrocarbon gas into contact with a catalyst together with water vapor and oxygen to burn and reform the hydrocarbon gas;
On the downstream side of the reforming step,
A heat exchange process for water heating that heats water as a water vapor source by heat exchange with the reformed gas;
A heat exchange process for heating a hydrocarbon gas that heats the hydrocarbon gas by heat exchange with the reformed gas,
Further, heating is performed in the hydrocarbon gas heating heat exchange step by heat exchange with the reformed gas upstream of the water heating heat exchange step and the hydrocarbon gas heating heat exchange step in the reformed gas path. Performing a raw material gas heating heat exchange step of heating a raw material gas which is a mixed gas of the hydrocarbon-based gas and water vapor obtained from the water heated in the water heating heat exchange step,
Further, the raw material gas supply step of supplying the raw material gas, the operation initial hydrogen generator reformer is not sufficiently rise in temperature, line physician raw material heating step of heating the raw material gas to be introduced into the reformer ,
Introducing oxygen gas in the raw material gas supply step without introducing oxygen gas in the water heating heat exchange step, hydrocarbon gas heating heat exchange step, raw material gas heating heat exchange step and raw material heating step A method for generating hydrogen.
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Publication number Priority date Publication date Assignee Title
JP5400425B2 (en) * 2009-03-03 2014-01-29 Jx日鉱日石エネルギー株式会社 Hydrogen production apparatus and fuel cell system
KR101394346B1 (en) * 2012-02-29 2014-05-14 성균관대학교산학협력단 Thermophotovoltaic apparatus having reformer for generating hydrogen
KR101487835B1 (en) 2014-03-13 2015-01-30 성균관대학교산학협력단 Thermophotovoltaic apparatus having reformer for generating hydrogen
CN104609369B (en) * 2015-01-30 2015-11-18 山东益丰生化环保股份有限公司 A kind ofly petroleum refinery is resolved the method that exhaust gas conversion becomes process for making hydrogen unstripped gas
CN104609368B (en) * 2015-01-30 2016-06-22 山东益丰生化环保股份有限公司 A kind of petroleum refinery is resolved the method that exhaust gas conversion becomes process for making hydrogen unstripped gas
CN106556668B (en) * 2015-09-30 2020-07-10 中国石油化工股份有限公司 Movable hydrocarbon steam conversion hydrogen production catalyst test platform and test method
TWI617508B (en) * 2016-11-21 2018-03-11 Huang Heng Xin Biogas catalyst cogeneration unit and operation method thereof
JP6944349B2 (en) * 2017-11-09 2021-10-06 エア・ウォーター株式会社 Hydrogen generator
KR102094646B1 (en) 2019-10-14 2020-03-30 주식회사 트리신 Highly efficient steam reforming hydrogen production apparatus with hydrodesulfurization

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4909808A (en) * 1987-10-14 1990-03-20 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Steam reformer with catalytic combustor
JPH05253436A (en) * 1992-03-16 1993-10-05 Mitsui Eng & Shipbuild Co Ltd Production of co gas free from ch4
JP2001151502A (en) * 1999-11-26 2001-06-05 Daikin Ind Ltd Fuel reforming device
US6485853B1 (en) * 2000-06-27 2002-11-26 General Motors Corporation Fuel cell system having thermally integrated, isothermal co-cleansing subsystem
JP2002050386A (en) * 2000-08-04 2002-02-15 Babcock Hitachi Kk Hydrogen producing device for fuel cell
JP2002274805A (en) * 2001-01-12 2002-09-25 Toyota Motor Corp Control of reformer having heat exchanger employing reform material as refrigerant
JP4968984B2 (en) * 2001-01-12 2012-07-04 三洋電機株式会社 Fuel cell reformer
JP2002293510A (en) * 2001-03-28 2002-10-09 Osaka Gas Co Ltd Carbon monoxide converter
JP2003103171A (en) * 2001-09-28 2003-04-08 Nippon Oil Corp Catalyst and method for auto thermal reforming, hydrogen producing device and fuel cell system
JP2003212508A (en) * 2002-01-24 2003-07-30 Honda Motor Co Ltd Method of controlling supply of water in reforming system
US20030192251A1 (en) * 2002-04-12 2003-10-16 Edlund David J. Steam reforming fuel processor
JP4175921B2 (en) * 2003-03-12 2008-11-05 東京瓦斯株式会社 Heat recovery system in hydrogen production equipment

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