JP2001163601A - Reforming device - Google Patents
Reforming deviceInfo
- Publication number
- JP2001163601A JP2001163601A JP34764199A JP34764199A JP2001163601A JP 2001163601 A JP2001163601 A JP 2001163601A JP 34764199 A JP34764199 A JP 34764199A JP 34764199 A JP34764199 A JP 34764199A JP 2001163601 A JP2001163601 A JP 2001163601A
- Authority
- JP
- Japan
- Prior art keywords
- reforming
- reaction
- section
- steam
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、原燃料と水成分を
水蒸気改質反応させて水素に富む改質ガスを生成する改
質部と、上記改質ガスに含有するＣＯを低減するシフト
反応部及び選択酸化部を備える改質装置に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reforming section for producing a reformed gas rich in hydrogen by subjecting a raw fuel and a water component to a steam reforming reaction, and a shift reaction for reducing CO contained in the reformed gas. The present invention relates to a reformer including a section and a selective oxidation section.
【０００２】[0002]
【従来の技術】従来から、燃料電池を構成する装置とし
て、水素に富んだ改質ガスを生成する改質装置が知られ
ている。上記改質装置は、原料と水成分を水蒸気改質反
応させて水素に富んだ改質ガスを生成する改質部と、上
記改質ガスに含有するＣＯを水性シフト反応により低減
させるシフト反応部と、さらにＣＯを選択的に酸化する
選択酸化部を備えるものである。例えば、特開平７−１
２６００１号公報に開示されている改質装置は、燃焼ガ
スを発生させる燃焼部の上に、上記改質部とシフト反応
部と選択酸化部がガスの流れ方向に沿って直列的に配列
された層と燃焼部からの燃焼ガスの流れる燃焼ガス流路
の層が交互に配置されて立ち上がる構造を有しているも
のである。上記改質部、シフト反応部、及び、選択酸化
部は、それぞれ触媒が充填され、この触媒を利用して、
ガス中の成分と反応させてガスを生成するものである。
そこで、上記改質部、シフト反応部、及び、選択酸化部
は、それぞれ触媒の反応に適した温度範囲に制御する必
要がある。2. Description of the Related Art Conventionally, a reformer for producing a hydrogen-rich reformed gas has been known as a device constituting a fuel cell. The reforming apparatus includes a reforming section that performs a steam reforming reaction of a raw material and a water component to generate a reformed gas rich in hydrogen, and a shift reaction section that reduces CO contained in the reformed gas by an aqueous shift reaction. And a selective oxidation unit for selectively oxidizing CO. For example, JP-A-7-1
In the reformer disclosed in Japanese Patent No. 26001, the reforming section, the shift reaction section, and the selective oxidizing section are arranged in series along the gas flow direction on a combustion section that generates combustion gas. It has a structure in which the layers and the layers of the combustion gas flow path through which the combustion gas flows from the combustion section are alternately arranged and stand up. The reforming section, shift reaction section, and selective oxidation section are each filled with a catalyst, and using this catalyst,
It reacts with components in gas to generate gas.
Therefore, it is necessary to control the reforming section, the shift reaction section, and the selective oxidation section within a temperature range suitable for the reaction of the catalyst.
【０００３】[0003]
【発明が解決しようとする課題】上記選択酸化部とし
て、ルテニウム系の触媒が注目されている。しかし、上
記選択酸化部に、ルテニウム系の触媒を用いる場合、酸
化反応に適する温度領域が２０〜４０℃程度の範囲と狭
く、また、改質部、シフト反応部の反応温度より低い温
度である。そのため、上記選択酸化部の温度調整は、改
質部、シフト反応部を通過した改質ガスを冷却すること
になるが、従来のファンによる冷却や低温の空気、水、
油等を触媒反応器の外面に接触させる手段では、冷却効
率が低いため、大型の冷却装置を必要としている。近年
の小型化の要望から、より容易に温度制御が可能である
装置が求められている。A ruthenium-based catalyst has attracted attention as the selective oxidation unit. However, when a ruthenium-based catalyst is used for the selective oxidation section, the temperature range suitable for the oxidation reaction is as narrow as about 20 to 40 ° C., and is lower than the reaction temperature of the reforming section and the shift reaction section. . Therefore, the temperature adjustment of the selective oxidizing section cools the reformed gas that has passed through the reforming section and the shift reaction section. However, cooling with a conventional fan or low-temperature air, water,
Means for bringing oil or the like into contact with the outer surface of the catalytic reactor requires a large-sized cooling device due to low cooling efficiency. In recent years, there has been a demand for a device capable of more easily controlling the temperature due to a demand for miniaturization.
【０００４】また、省エネルギーの高まりから、上記改
質部、シフト反応部、及び、選択酸化部の温度調整に用
いた熱エネルギーを、外部に排出する量を低減し、効率
的に利用することが求められている。[0004] Further, due to an increase in energy saving, it is necessary to reduce the amount of heat energy used for adjusting the temperature of the reforming section, the shift reaction section, and the selective oxidizing section to the outside, and to efficiently use the heat energy. It has been demanded.
【０００５】本発明は上記の事情に鑑みてなされたもの
で、その目的とするところは、選択酸化部の反応温度の
温度制御が容易であり、且つ、外部に排出する熱エネル
ギーを低減し、熱効率の良好な改質装置を提供すること
にある。The present invention has been made in view of the above circumstances, and has as its object to easily control the reaction temperature of the selective oxidizing unit and to reduce the heat energy discharged to the outside. An object of the present invention is to provide a reformer having good thermal efficiency.
【０００６】[0006]
【課題を解決するための手段】請求項１記載の改質装置
は、原燃料と水成分を水蒸気改質反応させて水素に富む
改質ガスを生成する改質部と、上記改質ガスに含有する
ＣＯを水性シフト反応により低減するシフト反応部と、
シフト反応部を通過した改質ガスのＣＯを選択的に酸化
する選択酸化部と、上記改質部に熱エネルギーとなる燃
焼ガスを供給する燃焼部を備える改質装置において、上
記選択酸化部の酸化反応の温度を、飽和した水または水
蒸気で調整する調整手段を備えると共に、この選択酸化
部を通過した飽和した水または水蒸気が、上記水蒸気改
質反応の水成分として改質部に導入する導入手段を備え
ることを特徴とする。上記によって、飽和状態の水また
は水蒸気は、その凝縮熱伝達率が１０００Ｗ／ｍ2 Ｋと
水と比較して大きいため、同量の水と比較し、僅かな飽
和状態の水があれば、上記酸化反応の温度を１００〜１
２０℃に制御することができるものであり、さらに、選
択酸化部を流れた飽和状態の水または水蒸気を、水蒸気
改質反応の水成分とするので、水蒸気改質反応の加温が
大幅に低減できるものである。According to the present invention, there is provided a reforming apparatus, comprising: a reforming section for performing a steam reforming reaction of a raw fuel and a water component to generate a hydrogen-rich reformed gas; A shift reaction section for reducing the contained CO by an aqueous shift reaction,
In a reforming apparatus including a selective oxidizing section that selectively oxidizes CO of the reformed gas that has passed through the shift reaction section, and a combustion section that supplies a combustion gas serving as thermal energy to the reforming section, An adjusting means for adjusting the temperature of the oxidation reaction with saturated water or steam is provided, and the saturated water or steam passed through the selective oxidation section is introduced into the reforming section as a water component of the steam reforming reaction. It is characterized by comprising means. As described above, the saturated heat transfer coefficient of water or water vapor is 1000 W / m 2 K, which is larger than that of water. Therefore, compared with the same amount of water, if there is a slight amount of saturated water, The temperature of the oxidation reaction is 100 to 1
The temperature can be controlled to 20 ° C. Further, since the saturated water or steam flowing through the selective oxidation section is used as the water component of the steam reforming reaction, the heating of the steam reforming reaction is greatly reduced. You can do it.
【０００７】請求項２記載の改質装置は、請求項１記載
の改質装置において、上記飽和した水または水蒸気は、
選択酸化部を通過した改質ガスの熱で水を蒸発すること
により発生させたものであることを特徴とする。上記に
よって、選択酸化部を通過した改質ガスの熱を用いて、
飽和した水または水蒸気を作製するので、改質ガスの熱
エネルギーを効率良く利用できるものである。According to a second aspect of the present invention, in the reformer of the first aspect, the saturated water or steam is
It is generated by evaporating water with the heat of the reformed gas that has passed through the selective oxidizing section. By the above, using the heat of the reformed gas passed through the selective oxidation section,
Since saturated water or steam is produced, the thermal energy of the reformed gas can be used efficiently.
【０００８】請求項３記載の改質装置は、請求項１記載
の改質装置において、上記飽和した水または水蒸気は、
上記改質部に水蒸気改質反応の熱エネルギーを供給した
燃焼ガスの熱で水を蒸発することにより発生させたもの
であることを特徴とする。上記によって、燃焼ガスの熱
を用いて、飽和した水または水蒸気を作製するので、燃
焼ガスの熱エネルギーを効率良く利用できるものであ
る。According to a third aspect of the present invention, in the reformer of the first aspect, the saturated water or steam is
It is characterized by being generated by evaporating water with the heat of the combustion gas that has supplied the thermal energy of the steam reforming reaction to the reforming section. As described above, since saturated water or water vapor is produced using the heat of the combustion gas, the thermal energy of the combustion gas can be used efficiently.
【０００９】請求項４記載の改質装置は、請求項１乃至
請求項３いずれか記載の改質装置において、上記選択酸
化部の酸化反応の温度を調整した飽和した水または水蒸
気を、水蒸気改質反応の水成分として改質部に導入する
前に、改質部で生成した、シフト反応部に導入する前の
改質ガスの熱で加熱することを特徴とする。上記によっ
て、選択酸化部を流れた飽和状態の水または水蒸気を、
水蒸気改質反応の水成分として導入する前に、改質ガス
の熱で加熱するので、水蒸気改質反応の反応温度にまで
加温する熱量が大幅に低減できるため、熱エネルギーを
効率的に利用したものとなっている。According to a fourth aspect of the present invention, in the reforming apparatus according to any one of the first to third aspects, the saturated water or steam in which the temperature of the oxidation reaction of the selective oxidizing section is adjusted is subjected to steam reforming. Before being introduced into the reforming section as a water component of the quality reaction, heating is performed by the heat of the reformed gas generated in the reforming section and before being introduced into the shift reaction section. By the above, the saturated water or steam flowing through the selective oxidation section is
Before being introduced as a water component in the steam reforming reaction, it is heated by the heat of the reformed gas, so the amount of heat to be heated to the reaction temperature of the steam reforming reaction can be greatly reduced, so heat energy is used efficiently It has become.
【００１０】[0010]
【発明の実施の形態】図１は、請求項１記載の改質装置
に対応する実施の形態の一例を示す概略図である。DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a schematic diagram showing an example of an embodiment corresponding to the reformer according to the first aspect.
【００１１】上記改質装置は、原燃料と水成分を水蒸気
改質反応させて水素に富む改質ガスを生成する改質部１
と、上記改質ガスに含有するＣＯを水性シフト反応によ
り低減するシフト反応部２と、シフト反応部２を通過し
た改質ガスのＣＯを選択的に酸化する選択酸化部３と、
上記改質部１に熱エネルギーとなる燃焼ガスを供給する
燃焼部４を備えている。The reforming unit includes a reforming unit 1 for producing a reformed gas rich in hydrogen by subjecting a raw fuel and a water component to a steam reforming reaction.
A shift reaction unit 2 that reduces CO contained in the reformed gas by an aqueous shift reaction, a selective oxidation unit 3 that selectively oxidizes CO of the reformed gas that has passed through the shift reaction unit 2,
A combustion section 4 for supplying a combustion gas serving as thermal energy to the reforming section 1 is provided.
【００１２】上記燃焼部４は、空気を含む燃料ガスの燃
焼により燃焼ガスを発生するものである。上記改質装置
は、上記燃焼部４で発生した燃焼ガスを、上記改質部１
に熱エネルギーとして供給すると共に、上記シフト反応
部２にも反応熱として熱エネルギーを供給できるよう
に、燃焼ガス流路５が形成されている。また、上記燃焼
ガスを発生するための燃焼手段としては、バーナーを用
いる方法、Ｐｔ、Ｒｕ、Ｐｄ、Ｒｈ等の燃焼触媒を担持
させたものを用いる方法が挙げられる。The combustion section 4 generates combustion gas by burning fuel gas containing air. The reformer converts the combustion gas generated in the combustion section 4 into the reforming section 1
The combustion gas flow path 5 is formed so that the shift reaction section 2 can be supplied with heat energy as reaction heat while supplying heat energy to the shift reaction section 2. Examples of the combustion means for generating the combustion gas include a method using a burner and a method using a catalyst carrying a combustion catalyst such as Pt, Ru, Pd, and Rh.
【００１３】上記改質部１は、改質触媒を充填してお
り、上記燃焼ガスから反応熱を得て原料と水成分とから
水蒸気改質反応により水素に富んだ改質ガスを生成する
ものである。上記改質触媒は、例えば、ニッケル系、ル
テニウム系、ロジウム系等の金属をアルミナやジルコニ
ア等からなる担体に担持させたものが例示される。改質
部１では、改質触媒の粒子間の隙間を、上記原料と水成
分の混合ガスが通り抜けるようになっており、このと
き、上記混合ガスが改質触媒に接触することにより水蒸
気改質反応が行われ、改質ガスを生成する。この水蒸気
改質反応は、燃焼ガスの熱エネルギーによって加熱さ
れ、反応熱が供給されるものである。上記原料として
は、メタノール等のアルコール系燃料や天然ガス、ブタ
ン、プロパン等の炭化水素系燃料のガスが利用される。
上記水蒸気改質反応は、原料としてブタンガスを用いた
場合、反応温度を５００℃以上とすると良好な反応が行
えるものである。The reforming section 1 is filled with a reforming catalyst, generates reaction heat from the combustion gas, and generates a hydrogen-rich reformed gas from a raw material and a water component by a steam reforming reaction. It is. Examples of the reforming catalyst include one in which a nickel-based, ruthenium-based, or rhodium-based metal is supported on a carrier made of alumina, zirconia, or the like. In the reforming section 1, the mixed gas of the raw material and the water component passes through the gap between the particles of the reforming catalyst, and at this time, the mixed gas comes into contact with the reforming catalyst, so that the steam reforming is performed. The reaction takes place to produce a reformed gas. This steam reforming reaction is heated by the thermal energy of the combustion gas to supply the reaction heat. Examples of the raw material include alcohol fuels such as methanol, and hydrocarbon fuel gases such as natural gas, butane, and propane.
In the above steam reforming reaction, when butane gas is used as a raw material, a favorable reaction can be performed when the reaction temperature is 500 ° C. or higher.
【００１４】上記シフト反応部２は、シフト触媒を充填
しており、上記改質ガスに含有するＣＯを水性シフト反
応により低減させるものである。上記シフト触媒は、例
えば、Ｃｕ、Ｚｎ、Ｆｅ、Ｃｒ等をアルミナやジルコニ
ア等からなる担体に担持させたものが例示される。シフ
ト反応部２では、改質部１にて生成した改質ガスがシフ
ト触媒に接触することにより、改質ガス中に含まれる一
酸化炭素と水蒸気が反応して水素と二酸化炭素になる水
性シフト反応が行われ、これにより改質ガス中の一酸化
炭素の大部分が除去される。上記水性シフト反応は、原
料としてブタンガスを用いた場合、反応温度を２００〜
２５０℃とすると良好な反応が行えるものである。The shift reaction section 2 is filled with a shift catalyst, and reduces CO contained in the reformed gas by an aqueous shift reaction. Examples of the shift catalyst include one in which Cu, Zn, Fe, Cr, or the like is supported on a carrier made of alumina, zirconia, or the like. In the shift reaction unit 2, the reformed gas generated in the reforming unit 1 comes into contact with the shift catalyst, so that carbon monoxide and water vapor contained in the reformed gas react with each other to form an aqueous shift to form hydrogen and carbon dioxide. A reaction takes place, which removes most of the carbon monoxide in the reformed gas. In the aqueous shift reaction, when butane gas is used as a raw material, the reaction temperature is 200 to
When the temperature is 250 ° C., a favorable reaction can be performed.
【００１５】上記選択酸化部３は、上記シフト反応部２
を通過した改質ガスに残存するＣＯを選択的に酸化する
ことで低減させるものである。上記選択酸化部３は、Ｃ
Ｏ酸化触媒として、例えば、Ｐｔ、Ｒｕ等をアルミナや
ジルコニア等からなる担体に担持させたものが例示され
る。上記選択酸化部３は、改質ガスがＣＯ酸化触媒と接
触して、ＣＯが選択的に酸化され、二酸化炭素となって
除去される。上記選択酸化の反応は、原料としてブタン
ガスを用い、ＣＯ酸化触媒としてＰｔとＲｕの混合触媒
を用いた場合、反応温度を１００〜１２０℃とすると良
好な反応が行える。The selective oxidizing section 3 includes the shift reaction section 2
Is reduced by selectively oxidizing the CO remaining in the reformed gas that has passed through. The selective oxidation section 3 is composed of C
As the O oxidation catalyst, for example, a catalyst in which Pt, Ru, or the like is supported on a carrier made of alumina, zirconia, or the like is exemplified. In the selective oxidizing section 3, the reformed gas comes into contact with the CO oxidation catalyst, so that the CO is selectively oxidized and removed as carbon dioxide. In the selective oxidation reaction, when butane gas is used as a raw material and a mixed catalyst of Pt and Ru is used as a CO oxidation catalyst, a favorable reaction can be performed at a reaction temperature of 100 to 120 ° C.
【００１６】本発明の改質装置にあっては、上記選択酸
化部３の酸化反応の温度を、飽和した水または水蒸気で
調整する調整手段を備えるものである。上記選択酸化部
３は、ＣＯ酸化触媒が充填し、改質ガスの流れる触媒層
６ａと、その外周に飽和した水または水蒸気が流れる流
路６ｂを備えている。上記流路６ｂは、入口に水を供給
する水供給ポンプ７、及び、ヒータ８を備え、このヒー
タ８で１００℃に加熱することにより、供給された水が
気化され、飽和状態の水または水蒸気となったものが流
れる。The reformer of the present invention is provided with adjusting means for adjusting the temperature of the oxidation reaction of the selective oxidation section 3 with saturated water or steam. The selective oxidation unit 3 includes a catalyst layer 6a filled with a CO oxidation catalyst and through which a reformed gas flows, and a flow path 6b around the periphery of which a saturated water or steam flows. The flow path 6b includes a water supply pump 7 for supplying water to an inlet, and a heater 8, and when the heater 8 is heated to 100 ° C., the supplied water is vaporized, and saturated water or steam is supplied. Is flowing.
【００１７】上記ＣＯが反応して、二酸化炭素を生成す
る場合、多大な発熱反応を伴う。例えば、１ｍｏｌのＣ
Ｏが反応すると、２８３ｋＪの発熱を伴うものである。
一方、上記飽和状態の水または水蒸気は、その凝縮熱伝
達率が１０００Ｗ／ｍ2 Ｋと水と比較して大きいため、
同量の水と比較し、僅かな飽和状態の水があれば、上記
酸化反応の温度を１００〜１２０℃に制御することがで
きるものである。上記改質装置は、選択酸化部３の酸化
反応の温度を飽和した水または水蒸気で調整するので、
酸化反応の温度制御が容易なものである。When the above-mentioned CO reacts to form carbon dioxide, it involves a large exothermic reaction. For example, 1 mol of C
When O reacts, it generates 283 kJ of heat.
On the other hand, the saturated water or water vapor has a heat transfer coefficient of condensation of 1000 W / m 2 K, which is larger than that of water.
Compared with the same amount of water, the temperature of the oxidation reaction can be controlled at 100 to 120 ° C. if there is a little saturated water. Since the reformer adjusts the temperature of the oxidation reaction of the selective oxidation unit 3 with saturated water or steam,
The temperature control of the oxidation reaction is easy.
【００１８】さらに、上記改質装置は、選択酸化部３を
通過した飽和した水または水蒸気が、水蒸気改質反応の
水成分として改質部１に導入されるものである。すなわ
ち、上記改質装置は、上記選択酸化部３の流路５ｂの出
口が、改質部１に導入される水成分の水成分導入路９に
接続している。上記改質装置は、選択酸化部３を流れた
飽和状態の水または水蒸気を、水蒸気改質反応の水成分
とするので、水蒸気改質反応の加温が大幅に低減できる
ため、熱エネルギーを効率的に利用することができるも
のである。Further, in the reforming apparatus, saturated water or steam that has passed through the selective oxidizing section 3 is introduced into the reforming section 1 as a water component of a steam reforming reaction. That is, in the reforming apparatus, the outlet of the flow path 5b of the selective oxidation section 3 is connected to the water component introduction path 9 for the water component introduced into the reforming section 1. The reformer uses the saturated water or steam flowing through the selective oxidizing section 3 as a water component of the steam reforming reaction, so that the heating of the steam reforming reaction can be greatly reduced. It can be used on a regular basis.
【００１９】図２は、請求項２記載の改質装置に対応す
る実施の形態の一例を示す概略図である。上記改質装置
と異なる点のみ説明する。上記改質装置にあっては、選
択酸化部３の酸化反応の温度を調整する、飽和した水ま
たは水蒸気が、改質ガスの熱で水を蒸発することにより
発生させたものである。上記改質装置は、選択酸化部３
を通過した改質ガスの流路１５に熱交換器１２を備えて
いる。上記熱交換器１２は、改質ガスの流路１５と、水
供給ポンプ１１で供給された水の流れる水路１６を備え
ており、改質ガスから水に熱が伝えられ、上記水が飽和
状態となるものである。上記飽和状態の水または水蒸気
は、上記選択酸化部３の水または水蒸気が流れる流路６
ｂに導入されるものである。上記改質ガスの熱を用い
て、飽和した水または水蒸気を作製するので、改質ガス
の熱エネルギーを効率良く利用できるものである。FIG. 2 is a schematic view showing an example of an embodiment corresponding to the reformer according to the second aspect. Only different points from the above reformer will be described. In the above reformer, saturated water or steam for adjusting the temperature of the oxidation reaction of the selective oxidation section 3 is generated by evaporating water with the heat of the reformed gas. The above-mentioned reformer has a selective oxidation unit 3
A heat exchanger 12 is provided in a flow path 15 for the reformed gas that has passed through the heat exchanger. The heat exchanger 12 includes a reformed gas passage 15 and a water passage 16 through which water supplied by the water supply pump 11 flows. Heat is transmitted from the reformed gas to water, and the water is saturated. It is what becomes. The water or steam in the saturated state is supplied to the flow path 6 through which the water or steam of the selective oxidation section 3 flows.
b. Since saturated water or steam is produced using the heat of the reformed gas, the heat energy of the reformed gas can be used efficiently.
【００２０】図３は、請求項３記載の改質装置に対応す
る実施の形態の一例を示す概略図である。上記改質装置
と異なる点のみ説明する。上記改質装置にあっては、選
択酸化部３の酸化反応の温度を調整する、飽和した水ま
たは水蒸気が、上記改質部１に水蒸気改質反応の熱エネ
ルギーを供給した燃焼ガスの熱で水を蒸発することによ
り発生させたものである。上記改質装置は、改質部１と
シフト反応部２間に設けられている燃焼ガス流路５に、
第２の熱交換器１４を備えている。上記第２の熱交換器
１４は、燃焼ガス流路５と、水供給ポンプ１３で供給さ
れた水の流れる水路１７を備えており、燃焼ガスから水
に熱が伝えられ、上記水が飽和状態となるものである。
上記飽和状態の水または水蒸気は、上記選択酸化部３の
水または水蒸気が流れる流路６ｂに導入されるものであ
る。上記燃焼ガスの熱を用いて、飽和した水または水蒸
気を作製するので、燃焼ガスの熱エネルギーを効率良く
利用できるものである。FIG. 3 is a schematic view showing an example of an embodiment corresponding to the reformer according to the third aspect. Only different points from the above reformer will be described. In the above reformer, the saturated water or steam that adjusts the temperature of the oxidation reaction of the selective oxidation section 3 is heated by the heat of the combustion gas that supplies the heat energy of the steam reforming reaction to the reforming section 1. It is generated by evaporating water. The above-described reformer includes a combustion gas passage 5 provided between the reformer 1 and the shift reactor 2,
A second heat exchanger 14 is provided. The second heat exchanger 14 includes a combustion gas flow path 5 and a water passage 17 through which water supplied by the water supply pump 13 flows. Heat is transmitted from the combustion gas to the water, and the water is saturated. It is what becomes.
The water or steam in the saturated state is introduced into the flow path 6b of the selective oxidation unit 3 through which the water or steam flows. Since saturated water or steam is produced using the heat of the combustion gas, the heat energy of the combustion gas can be used efficiently.
【００２１】図４は、請求項２、３、４記載の改質装置
に対応する実施の形態の一例を示す概略図である。上記
改質装置と異なる点のみ説明する。上記改質装置にあっ
ては、選択酸化部３の酸化反応の温度を調整する、飽和
した水または水蒸気は、図２と同様の改質ガスの熱で水
を蒸発したものと、図３と同様の燃焼ガスの熱で水を蒸
発したものを用いるものである。上記改質装置は、水供
給ポンプ２３で供給された水が、三方弁２４を介して、
第１の水路１６と、第２の水路１７とに分岐している。
上記第１の水路１６は、選択酸化部３を通過した改質ガ
スの流路１５と熱交換するため第１の熱交換器１２に導
入される。上記第２の水路１７は、改質部１とシフト反
応部２間に設けられている燃焼ガス流路５と熱交換する
ため第２の熱交換器１４に導入される。上記第１の熱交
換器１２及び第２の熱交換器１４で水に熱エネルギーが
供給され、飽和状態となる。この飽和状態となった水ま
たは水蒸気は、選択酸化部３の入口の合流点２５で合流
し、上記選択酸化部３の水または水蒸気が流れる流路６
ｂに導入されるものである。FIG. 4 is a schematic view showing an example of an embodiment corresponding to the reformer according to the second, third and fourth aspects. Only different points from the above reformer will be described. In the above reformer, the saturated water or steam for adjusting the temperature of the oxidation reaction of the selective oxidizing section 3 is obtained by evaporating water with the heat of the reformed gas as in FIG. In this case, water obtained by evaporating water with the heat of a similar combustion gas is used. In the reformer, the water supplied by the water supply pump 23 is supplied through the three-way valve 24,
It branches into a first water channel 16 and a second water channel 17.
The first water passage 16 is introduced into the first heat exchanger 12 to exchange heat with the reformed gas passage 15 that has passed through the selective oxidation unit 3. The second water passage 17 is introduced into the second heat exchanger 14 for exchanging heat with the combustion gas passage 5 provided between the reforming section 1 and the shift reaction section 2. Heat energy is supplied to water in the first heat exchanger 12 and the second heat exchanger 14, and the water is saturated. The saturated water or steam joins at a junction 25 at the inlet of the selective oxidizing unit 3, and flows into the channel 6 where the water or steam of the selective oxidizing unit 3 flows.
b.
【００２２】さらに、上記改質装置は、上記選択酸化部
３の酸化反応の温度を調整した飽和した水または水蒸気
が、水蒸気改質反応の水成分として改質部１に導入され
る経路２６に、第３の熱交換器２１、及び、第４の熱交
換器２２を備える。上記第３の熱交換器２１は、上記経
路２６と、改質部１を通過した改質ガスが流れる第１の
改質ガス流路２７を備えており、改質ガスから上記水ま
たは水蒸気に熱が伝わる。上記第４の熱交換器２２は、
上記経路２６と、シフト反応部２を通過した改質ガスが
流れる第２の改質ガス流路２８を備えており、改質ガス
から上記水または水蒸気に熱が伝わる。上記改質装置
は、選択酸化部３を通過した飽和状態の水または水蒸気
を、水蒸気改質反応の水成分として導入する前に、改質
部１で生成した改質ガスの熱で加熱するので、水蒸気改
質反応の反応温度にまで加温する熱量が大幅に低減でき
るため、熱エネルギーを効率的に利用したものとなって
いる。Further, the reforming device is connected to the passage 26 through which the saturated water or steam whose temperature of the oxidation reaction of the selective oxidation section 3 is adjusted is introduced into the reforming section 1 as a water component of the steam reforming reaction. , A third heat exchanger 21, and a fourth heat exchanger 22. The third heat exchanger 21 includes the path 26 and a first reformed gas passage 27 through which the reformed gas that has passed through the reforming section 1 flows. Heat is transmitted. The fourth heat exchanger 22 includes:
A second reformed gas passage 28 through which the reformed gas having passed through the shift reaction section 2 flows is provided, and heat is transmitted from the reformed gas to the water or steam. The reformer heats the water or steam in the saturated state that has passed through the selective oxidizing unit 3 with the heat of the reformed gas generated in the reforming unit 1 before introducing it as the water component of the steam reforming reaction. In addition, the amount of heat to be heated to the reaction temperature of the steam reforming reaction can be greatly reduced, so that heat energy is efficiently used.
【００２３】また、上記第３の熱交換器２１、及び、第
４の熱交換器２２は、上記改質装置のように両方備えて
も良いし、片方備えたものでもよい。片方のみ備える場
合は、熱交換する温度差大きい第３の熱交換器２１が、
熱効率の点で良好である。Further, the third heat exchanger 21 and the fourth heat exchanger 22 may be provided both as in the above-described reformer, or may be provided in one of them. When only one is provided, the third heat exchanger 21 having a large temperature difference for heat exchange is
Good in terms of thermal efficiency.
【００２４】[0024]
【発明の効果】請求項１記載の改質装置は、選択酸化部
の酸化反応の温度を飽和した水または水蒸気で調整する
調整手段を備えるので、僅かな飽和状態の水があれば、
上記酸化反応の温度を制御することができるものであ
り、さらに、選択酸化部を流れた飽和状態の水または水
蒸気を、水蒸気改質反応の水成分とするので、水蒸気改
質反応の加温が大幅に低減できるものである。したがっ
て、上記改質装置は、選択酸化部の反応温度の温度制御
が容易であり、且つ、外部に排出する熱エネルギーを低
減した熱効率の良好なものである。According to the first aspect of the present invention, the reformer is provided with adjusting means for adjusting the temperature of the oxidation reaction of the selective oxidizing section with saturated water or steam.
It is possible to control the temperature of the oxidation reaction, and furthermore, the saturated water or steam flowing through the selective oxidation section is used as the water component of the steam reforming reaction, so that the heating of the steam reforming reaction is reduced. It can be greatly reduced. Therefore, the reforming apparatus is easy in temperature control of the reaction temperature of the selective oxidizing section, and has good thermal efficiency with reduced heat energy discharged to the outside.
【００２５】さらに、請求項２記載の改質装置は、特
に、選択酸化部を通過した改質ガスの熱を用いて、飽和
した水または水蒸気を作製するので、改質ガスの熱エネ
ルギーを効率良く利用できる。Furthermore, in the reformer according to the second aspect, since saturated water or steam is produced using the heat of the reformed gas passed through the selective oxidizing section, the heat energy of the reformed gas can be efficiently used. Can be used well.
【００２６】さらに、請求項３記載の改質装置は、特
に、水蒸気改質反応の熱エネルギーを供給した燃焼ガス
の熱を用いて、飽和した水または水蒸気を作製するの
で、燃焼ガスの熱エネルギーを効率良く利用できる。Furthermore, the reformer according to the third aspect produces saturated water or steam using the heat of the combustion gas supplied with the heat energy of the steam reforming reaction. Can be used efficiently.
【００２７】さらに、請求項４記載の改質装置は、特
に、選択酸化部を流れた飽和状態の水または水蒸気を、
水蒸気改質反応の水成分として導入する前に、改質ガス
の熱で加熱するので、水蒸気改質反応の反応温度にまで
加温する熱量が大幅に低減できるため、熱エネルギーを
効率的に利用したものとなっている。Furthermore, the reformer according to the fourth aspect of the present invention is preferably configured such that saturated water or steam flowing through the selective oxidation unit is
Before being introduced as a water component in the steam reforming reaction, it is heated by the heat of the reformed gas, so the amount of heat to be heated to the reaction temperature of the steam reforming reaction can be greatly reduced, so heat energy is used efficiently It has become.
【図１】本発明の改質装置の実施の形態の一例を示す概
略図である。FIG. 1 is a schematic diagram showing an example of an embodiment of a reformer of the present invention.
【図２】本発明の改質装置の他の実施の形態の一例を示
す概略図である。FIG. 2 is a schematic diagram showing an example of another embodiment of the reforming apparatus of the present invention.
【図３】本発明の改質装置の他の実施の形態の一例を示
す概略図である。FIG. 3 is a schematic diagram showing an example of another embodiment of the reforming apparatus of the present invention.
【図４】本発明の改質装置の他の実施の形態の一例を示
す概略図である。FIG. 4 is a schematic diagram showing an example of another embodiment of the reforming apparatus of the present invention.
１ 改質部 ２ シフト反応部 ３ 選択酸化部 ４ 燃焼部 ５ 燃焼ガス流路 ６ａ 触媒層 ６ｂ 流路 ９ 水成分導入路 DESCRIPTION OF SYMBOLS 1 Reforming part 2 Shift reaction part 3 Selective oxidation part 4 Combustion part 5 Combustion gas flow path 6a Catalyst layer 6b Flow path 9 Water component introduction path
───────────────────────────────────────────────────── フロントページの続き (72)発明者 薮ノ内 伸晃 大阪府門真市大字門真1048番地松下電工株 式会社内 Ｆターム(参考） 4G040 EA01 EA06 EB14 EB32 EB42 EB43 EB44 EC02 EC03 5H027 AA02 BA01 BA17 KK42 MM14 ────────────────────────────────────────────────── ─── Continued from the front page (72) Nobuaki Yabunouchi, Inventor No. 1048, Kadoma, Kadoma, Osaka Pref. MM14
Claims (4)
水素に富む改質ガスを生成する改質部と、上記改質ガス
に含有するＣＯを水性シフト反応により低減するシフト
反応部と、シフト反応部を通過した改質ガスのＣＯを選
択的に酸化する選択酸化部と、上記改質部に熱エネルギ
ーとなる燃焼ガスを供給する燃焼部を備える改質装置に
おいて、上記選択酸化部の酸化反応の温度を、飽和した
水または水蒸気で調整する調整手段を備えると共に、こ
の選択酸化部を通過した飽和した水または水蒸気が、上
記水蒸気改質反応の水成分として改質部に導入する導入
手段を備えることを特徴とする改質装置。1. A reforming section for producing a reformed gas rich in hydrogen by subjecting a raw fuel and a water component to a steam reforming reaction, and a shift reaction section for reducing CO contained in the reformed gas by an aqueous shift reaction. A selective oxidizing unit that selectively oxidizes CO of the reformed gas that has passed through the shift reaction unit; and a combustion unit that supplies a combustion gas serving as thermal energy to the reforming unit. And an adjusting means for adjusting the temperature of the oxidation reaction with saturated water or steam, and the saturated water or steam passing through the selective oxidation section is introduced into the reforming section as a water component of the steam reforming reaction. A reforming device comprising an introduction means.
化部を通過した改質ガスの熱で水を蒸発することにより
発生させたものであることを特徴とする請求項１記載の
改質装置。2. The reformer according to claim 1, wherein the saturated water or steam is generated by evaporating water with heat of the reformed gas passed through the selective oxidizing section. .
質部に水蒸気改質反応の熱エネルギーを供給した燃焼ガ
スの熱で水を蒸発することにより発生させたものである
ことを特徴とする請求項１記載の改質装置。3. The method according to claim 1, wherein the saturated water or steam is generated by evaporating water with heat of a combustion gas that supplies heat energy of a steam reforming reaction to the reforming section. The reforming apparatus according to claim 1.
した飽和した水または水蒸気を、水蒸気改質反応の水成
分として改質部に導入する前に、改質部で生成した、シ
フト反応部に導入する前の改質ガスの熱で加熱すること
を特徴とする請求項１乃至請求項３いずれか記載の改質
装置。4. A shift reaction generated in the reforming section before introducing saturated water or steam in which the temperature of the oxidation reaction of the selective oxidation section is adjusted as a water component of the steam reforming reaction into the reforming section. The reforming apparatus according to any one of claims 1 to 3, wherein the reforming apparatus is heated by heat of the reformed gas before being introduced into the section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34764199A JP3812253B2 (en) | 1999-12-07 | 1999-12-07 | Reformer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34764199A JP3812253B2 (en) | 1999-12-07 | 1999-12-07 | Reformer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001163601A true JP2001163601A (en) | 2001-06-19 |
| JP3812253B2 JP3812253B2 (en) | 2006-08-23 |
Family
ID=18391605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34764199A Expired - Lifetime JP3812253B2 (en) | 1999-12-07 | 1999-12-07 | Reformer |
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| Country | Link |
|---|---|
| JP (1) | JP3812253B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005093345A (en) * | 2003-09-19 | 2005-04-07 | Aisin Seiki Co Ltd | Fuel cell system |
| JP2005335996A (en) * | 2004-05-26 | 2005-12-08 | Idemitsu Kosan Co Ltd | Hydrogen producing system, fuel cell system, and hydrogen producing method |
| US7635399B2 (en) | 2003-06-27 | 2009-12-22 | Ebara Corporation | Fuel reformer |
| KR100979572B1 (en) | 2007-09-03 | 2010-09-02 | 주식회사 엘지화학 | System for reforming fuel |
| KR101071804B1 (en) | 2007-12-21 | 2011-10-11 | 주식회사 엘지화학 | Reactor for reforming fuel |
-
1999
- 1999-12-07 JP JP34764199A patent/JP3812253B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7635399B2 (en) | 2003-06-27 | 2009-12-22 | Ebara Corporation | Fuel reformer |
| JP2005093345A (en) * | 2003-09-19 | 2005-04-07 | Aisin Seiki Co Ltd | Fuel cell system |
| JP2005335996A (en) * | 2004-05-26 | 2005-12-08 | Idemitsu Kosan Co Ltd | Hydrogen producing system, fuel cell system, and hydrogen producing method |
| JP4551696B2 (en) * | 2004-05-26 | 2010-09-29 | 出光興産株式会社 | Hydrogen production system, fuel cell system, and hydrogen production method |
| KR100979572B1 (en) | 2007-09-03 | 2010-09-02 | 주식회사 엘지화학 | System for reforming fuel |
| KR101071804B1 (en) | 2007-12-21 | 2011-10-11 | 주식회사 엘지화학 | Reactor for reforming fuel |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3812253B2 (en) | 2006-08-23 |
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