JP5423180B2 - Hydrogen generator - Google Patents
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- JP5423180B2 JP5423180B2 JP2009151962A JP2009151962A JP5423180B2 JP 5423180 B2 JP5423180 B2 JP 5423180B2 JP 2009151962 A JP2009151962 A JP 2009151962A JP 2009151962 A JP2009151962 A JP 2009151962A JP 5423180 B2 JP5423180 B2 JP 5423180B2
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本発明は、改質触媒を用いて、原料と水蒸気との改質反応により水素含有ガスを生成させる水素生成装置に関するものである。 The present invention relates to a hydrogen generator that generates a hydrogen-containing gas by a reforming reaction between a raw material and steam using a reforming catalyst.
近年、小型装置でも高効率な発電を可能とする燃料電池発電システムは、分散型エネルギー供給源の発電システムとして開発が進められている。発電時の燃料となる水素ガス又は水素含有ガスは、一般的なインフラとして整備されていない。そこで、例えば都市ガス、プロパンガス等の既存の化石原料インフラから供給される原料を利用し、それらの原料と水蒸気（水）との改質反応により水素含有ガスを生成させる水素生成装置が併設される。 In recent years, fuel cell power generation systems that enable highly efficient power generation even with small devices have been developed as power generation systems for distributed energy sources. Hydrogen gas or hydrogen-containing gas used as fuel during power generation has not been developed as a general infrastructure. For this reason, for example, a hydrogen generator that uses raw materials supplied from existing fossil raw material infrastructure such as city gas and propane gas, and generates hydrogen-containing gas by reforming reaction of those raw materials and steam (water) is additionally provided. The
一般的に水素生成装置は、原料と水とを改質反応させ、水素含有ガスを生成させる改質部を備える。また、水素含有ガス中の一酸化炭素を低減させる一酸化炭素低減部となる、一酸化炭素と水蒸気を水性ガスシフト反応させる変成部、および一酸化炭素を酸化させる選択酸化部を設ける構成がとられることが多い。それらの反応部には、各反応に適した触媒、例えば、改質部にはＲｕ触媒やＮｉ触媒、変成部にはＣｕ−Ｚｎ触媒、選択酸化部にはＲｕ触媒等が用いられている。また、各反応部には適した温度があり、改質部は６５０℃程度、変成部は２００℃程度、選択酸化部は１５０℃程度で使用されることが多い。 Generally, a hydrogen generator includes a reforming unit that causes a reforming reaction between a raw material and water to generate a hydrogen-containing gas. In addition, a configuration is provided in which a carbon monoxide reduction unit that reduces carbon monoxide in the hydrogen-containing gas, a shift unit that performs a water gas shift reaction between carbon monoxide and water vapor, and a selective oxidation unit that oxidizes carbon monoxide. There are many cases. In these reaction parts, a catalyst suitable for each reaction, for example, a Ru catalyst or Ni catalyst is used in the reforming part, a Cu-Zn catalyst is used in the shift part, and a Ru catalyst is used in the selective oxidation part. Each reaction section has a suitable temperature, and the reforming section is often used at about 650 ° C., the modification section is about 200 ° C., and the selective oxidation section is used at about 150 ° C.
さて、燃料電池発電システムを家庭用途で使用する場合、家庭での電力負荷に合わせ、日々起動停止運転を行うことで、高いエネルギー効率での運転が可能となる。ただ、起動停止運転は、燃料電池発電システムに大きな負担をかける。特に、水素生成装置は、高温での運転と、常温への冷却が繰り返されるので、大きな熱ひずみが日々加わることになる。その結果、装置内の触媒が粉化し、粉塵を発生させてしまう。粉塵化することで反応器から流出し、触媒反応に寄与しなくなるのを防止するため、改質管にフィルターを設けて、その粉塵の流出を防止する構成が考案されている（例えば、特許文献１参照）。 Now, when the fuel cell power generation system is used for home use, it is possible to operate with high energy efficiency by performing the start / stop operation every day according to the power load at home. However, start / stop operation places a heavy burden on the fuel cell power generation system. Particularly, since the hydrogen generator is repeatedly operated at a high temperature and cooled to room temperature, a large thermal strain is applied every day. As a result, the catalyst in the apparatus is pulverized to generate dust. In order to prevent the dust from flowing out from the reactor and not contributing to the catalytic reaction, a structure has been devised in which a filter is provided in the reforming tube to prevent the dust from flowing out (for example, Patent Documents). 1).
また、反応部内の触媒の一部が圧壊し、改質反応ガス（水素含有ガス）の流路が閉塞気味になるのを防止するため、反応部に仕切部材を設けて、触媒の圧壊を防止する構成が考案されている（例えば、特許文献２参照）。 In addition, in order to prevent a part of the catalyst in the reaction part from collapsing and the flow path of the reforming reaction gas (hydrogen-containing gas) to become obstructive, a partition member is provided in the reaction part to prevent the catalyst from collapsing. The structure which does is devised (for example, refer patent document 2).
前記従来の改質管にフィルターを設けて、その粉塵の流出を防止する構成では、粉塵の流出を防止できる。しかし、フィルターが目詰まりして、水素含有ガスの流路が閉塞することには、対応できない。また、仕切部材を設けた構成でも、完全には触媒の圧壊を防止することができず、粉塵が発生して、水素含有ガスの流路を閉塞する可能性がある。 In the configuration in which a filter is provided in the conventional reforming tube to prevent the dust from flowing out, the dust can be prevented from flowing out. However, it cannot cope with clogging of the filter and blocking of the flow path of the hydrogen-containing gas. In addition, even with the configuration in which the partition member is provided, it is not possible to completely prevent the catalyst from being crushed, and dust may be generated to block the hydrogen-containing gas flow path.
本発明は、前記従来の課題を解決するもので、起動停止に伴い水素生成装置で発生する触媒の粉塵を、効果的に捕塵して、粉塵による流路閉塞を抑制する水素生成装置を提供することを目的とする。 The present invention solves the above-described conventional problems, and provides a hydrogen generation device that effectively captures catalyst dust generated in the hydrogen generation device when starting and stopping and suppresses blockage of the flow path due to dust. The purpose is to do.
上記の課題を解決するため、本発明は、底板を備える内筒と、貫通孔が設けられる底板を備え、内筒の外側に配される中筒と、底板を備え、中筒の外側に配される外筒と、少なくとも内筒と中筒との間で構成される空間に、原料と水蒸気とを改質反応させ水素含有ガスを生成させる改質触媒が保持されており、改質触媒の粉塵が、重力により内筒の底板と中筒の底板との間で構成される空間に落下する水素生成装置であって、内筒の底板と中筒の底板との間で構成される空間に、水素含有ガスの流路となる貫通孔よりも水素含有ガスの上流側で粉塵を捕塵する捕塵部を設けたのである。 In order to solve the above problems, the present invention includes an inner cylinder including a bottom plate, a bottom plate provided with a through hole, a middle cylinder disposed outside the inner cylinder, a bottom plate, and disposed outside the middle cylinder. A reforming catalyst that generates a hydrogen-containing gas by reforming the raw material and steam is held in a space formed between the outer cylinder and at least the inner cylinder and the middle cylinder . A hydrogen generation device in which dust falls into a space formed between the bottom plate of the inner cylinder and the bottom plate of the middle cylinder by gravity, and in a space configured between the bottom plate of the inner cylinder and the bottom plate of the middle cylinder , Ru Nodea provided with a dust trapping portion for dust trapping dust upstream of the hydrogen-containing gas than the through-hole serving as a flow path of the hydrogen-containing gas.
本発明の水素生成装置は、内筒の底板と中筒の底板との間で構成される空間に、水素含有ガスの流路となる貫通孔よりも水素含有ガスの上流側で粉塵を捕塵する捕塵部を設けたことにより、捕塵部から水素含有ガスの下流側に粉塵が流出することを抑制して、中筒の底板に設けられる貫通孔近傍での粉塵の堆積を低減でき、相対的に水素含有ガスの通過断面積が小さくなる貫通孔近傍で、水素含有ガスの流路が閉塞する可能性を低減できる。 Hydrogen generator of the present invention, the space formed between the bottom plate of the bottom plate and the middle cylinder of the inner cylinder, dust trapping dust upstream of the hydrogen-containing gas than the through-hole serving as a flow path of the hydrogen-containing gas By providing the dust trapping part, it is possible to suppress the dust from flowing out from the dust trapping part to the downstream side of the hydrogen-containing gas, and to reduce the accumulation of dust in the vicinity of the through hole provided in the bottom plate of the middle cylinder , in the through-holes near the passage sectional area of relatively hydrogen-containing gas is reduced, thereby reducing the likelihood that the flow path of the hydrogen-containing gas is closed.
第１の発明は、底板を備える内筒と、貫通孔が設けられる底板を備え、前記内筒の外側に配される中筒と、底板を備え、前記中筒の外側に配される外筒と、少なくとも前記内筒と前記中筒との間で構成される空間に、原料と水蒸気とを改質反応させ水素含有ガスを生成させる改質触媒が保持されており、前記改質触媒の粉塵が、重力により前記内筒の底板
と前記中筒の底板との間で構成される空間に落下する水素生成装置であって、前記内筒の底板と前記中筒の底板との間で構成される空間に、前記水素含有ガスの流路となる前記貫通孔よりも前記水素含有ガスの上流側で前記粉塵を捕塵する捕塵部を設けたのである。
1st invention is provided with the inner cylinder provided with a baseplate, the baseplate provided with a through-hole, the middle cylinder distribute | arranged to the outer side of the said inner cylinder, the outer cylinder provided with the baseplate and distribute | arranged on the outer side of the said intermediate cylinder A reforming catalyst for reforming the raw material and water vapor to generate a hydrogen-containing gas is held in a space formed between at least the inner cylinder and the middle cylinder, and the dust of the reforming catalyst But the bottom plate of the inner cylinder by gravity
And a bottom plate of the inner cylinder , and a hydrogen generator that falls into a space formed between the inner cylinder and the bottom plate of the inner cylinder. than the through-hole serving as a flow path Ru Nodea provided with a dust trapping portion for dust trapping the dust in the upstream side of the hydrogen-containing gas.
第２の発明は、特に、第１の発明において、前記捕塵部は、前記中筒の底板に設けられ、前記内筒の底板方向に凸形状を有する突起部で構成される。 In a second aspect of the invention, in particular, in the first aspect of the invention, the dust catching portion is provided on a bottom plate of the middle cylinder, and includes a protrusion having a convex shape in the bottom plate direction of the inner cylinder.
第３の発明は、特に、第２の発明において、前記突起部は、前記改質触媒が保持されている方向に向けてフランジ部を備える。 In a third aspect of the invention, in particular, in the second aspect of the invention, the protrusion includes a flange portion in a direction in which the reforming catalyst is held.
第４の発明は、特に、第１の発明において、前記捕塵部は、前記中筒の底板に設けられるリブで構成される。 In a fourth aspect of the invention, in particular, in the first aspect of the invention, the dust catcher is configured by a rib provided on the bottom plate of the middle cylinder.
第５の発明は、特に、第４の発明において、前記リブは、前記内筒の底板に向けて凸となるように構成される。 According to a fifth aspect of the invention, in particular, in the fourth aspect of the invention, the rib is configured to be convex toward the bottom plate of the inner cylinder.
第６の発明は、特に、第１の発明において、前記捕塵部は、前記内筒の底板に向けて凸となるように、前記貫通孔に設けられるバーリング部で構成される。 In a sixth aspect of the invention, in particular, in the first aspect of the invention, the dust catching portion is constituted by a burring portion provided in the through hole so as to protrude toward the bottom plate of the inner cylinder.
第７の発明は、特に、第６の発明において、前記バーリング部は、前記改質触媒が保持されている方向に向けてフランジ部を備える。 In a seventh aspect of the invention, in particular, in the sixth aspect of the invention, the burring portion includes a flange portion in a direction in which the reforming catalyst is held.
第８の発明は、特に、第１から７のいずれか１つの発明において、前記捕塵部と前記内筒の底板との間で、前記内筒の底板と前記中筒の底板との間で構成される空間における狭隘部が構成され、前記狭隘部での前記水素含有ガスの通過断面積が、前記貫通孔での前記水素含有ガスの通過断面積より大きくなるように、前記捕塵部が設けられている。 In an eighth aspect of the invention, in particular, in any one of the first to seventh aspects of the invention, between the dust collecting portion and the bottom plate of the inner cylinder, between the bottom plate of the inner cylinder and the bottom plate of the middle cylinder. A narrow portion in the space to be configured is configured , and the dust capturing unit is configured such that a passage cross-sectional area of the hydrogen-containing gas in the narrow portion is larger than a cross-sectional area of the hydrogen-containing gas in the through hole. Is provided.
第９の発明は、特に、第１から８のいずれか１つの発明において、前記捕塵部は、前記中筒の底板の全周方向に連続して設けられる。 In a ninth aspect of the invention, in particular, in any one of the first to eighth aspects of the invention, the dust catcher is continuously provided in the entire circumferential direction of the bottom plate of the middle cylinder.
第１０の発明は、特に、第１から９のいずれか１つの発明において、前記内筒と、前記中筒と、前記外筒は、略同心円形状に配置される。 In a tenth aspect of the invention, in particular, in any one of the first to ninth aspects, the inner cylinder, the middle cylinder, and the outer cylinder are arranged in a substantially concentric shape.
第１１の発明は、特に、第１から１０のいずれか１つの発明において、少なくとも前記改質触媒を加熱する加熱部を備え、前記加熱部は、前記内筒の内側に設けられる。 In an eleventh aspect of the invention, in particular, in any one of the first to tenth aspects of the invention, the eleventh aspect includes at least a heating unit that heats the reforming catalyst, and the heating unit is provided inside the inner cylinder.
第１２の発明は、特に、第１から１１のいずれか１つの発明において、前記内筒および前記中筒の少なくとも一方の側面に設けられる棚段により、前記改質触媒が保持されている。 In a twelfth aspect of the invention, in particular, in any one of the first to eleventh aspects, the reforming catalyst is held by a shelf provided on at least one side of the inner cylinder and the middle cylinder.
以下、本発明を実施の形態について、図面を参照しながら説明する。なお、本実施の形態によって本発明が限定されるものではない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the present embodiment.
（実施の形態１）
図１は、本発明の第１の実施の形態における水素生成装置の要部断面図である。
(Embodiment 1)
FIG. 1 is a cross-sectional view of a main part of a hydrogen generator according to a first embodiment of the present invention.
図１において、水素生成装置１は、内筒底板６を備えた内筒５の外側に、中筒底板８を備えた中筒７が配置されている。その中筒７の外側には、外筒底板１６を備えた外筒１５が配置されている。内筒５と、中筒７と、外筒１５が略同心円形状に配置されている。中筒底板８には、その中央部分に、貫通孔９を備える。また、中筒７の側面からその貫通孔９にいたる中筒底板８に、内筒の底板方向に凸形状を有し、全周方向に連続した形状で、円筒状の突起部１０が設けられている。その突起部１０と、内筒底板６との間で、内筒底板６と中筒底板８との空間における狭隘部１１が構成されている。なお、内筒５と、中筒７と、外筒１５の上方部分は、それぞれが適切に接続され、略円筒形状の反応器が構成されている（上方部分の、詳細な接続関係の説明は、省略する）。 In FIG. 1, in the hydrogen generator 1, an intermediate cylinder 7 having an intermediate cylinder bottom plate 8 is arranged outside an inner cylinder 5 having an inner cylinder bottom plate 6. An outer cylinder 15 having an outer cylinder bottom plate 16 is disposed outside the middle cylinder 7. The inner cylinder 5, the middle cylinder 7, and the outer cylinder 15 are arranged in a substantially concentric shape. The middle cylinder bottom plate 8 is provided with a through hole 9 at the center thereof. Further, a cylindrical projection 10 is provided on the middle cylinder bottom plate 8 extending from the side surface of the middle cylinder 7 to the through hole 9 in a shape that has a convex shape in the direction of the bottom plate of the inner cylinder and is continuous in the entire circumferential direction. ing. A narrow portion 11 in the space between the inner cylinder bottom plate 6 and the middle cylinder bottom plate 8 is formed between the protruding portion 10 and the inner cylinder bottom plate 6. In addition, the upper part of the inner cylinder 5, the inner cylinder 7, and the outer cylinder 15 are each appropriately connected to form a substantially cylindrical reactor (the detailed connection relationship of the upper part is described). , Omitted).
その水素生成装置１は、水供給経路３から供給される水を蒸発させるとともに、原料と水蒸気の混合ガスを予熱する予熱部２３を備える。また、原料供給経路４から供給される原料と、水蒸気との改質反応を進行させる水蒸気改質部２０と、水蒸気改質部２０で生成した水素含有ガス中の一酸化炭素と水蒸気とを変成反応させて、水素含有ガスの一酸化炭素濃度を低減させる変成部２５を有している。また、変成部２５を通過した後の水素含有ガス中に残留する一酸化炭素を、空気供給部１９から変成部２５を通過した後の水素含有ガスに供給される空気を用いて、主に酸化させて除去する選択酸化部２６を有している。なお、変成部２５、選択酸化部２６により、一酸化炭素低減部が構成されている。 The hydrogen generator 1 includes a preheating unit 23 that evaporates water supplied from the water supply path 3 and preheats a mixed gas of raw material and water vapor. In addition, a steam reforming unit 20 that promotes a reforming reaction between the raw material supplied from the raw material supply path 4 and steam, and carbon monoxide and steam in the hydrogen-containing gas generated in the steam reforming unit 20 are transformed. There is a shift section 25 that reacts to reduce the carbon monoxide concentration of the hydrogen-containing gas. Further, the carbon monoxide remaining in the hydrogen-containing gas after passing through the shift conversion section 25 is mainly oxidized using air supplied from the air supply section 19 to the hydrogen-containing gas after passing through the shift conversion section 25. The selective oxidation unit 26 is removed. The metamorphic unit 25 and the selective oxidation unit 26 constitute a carbon monoxide reduction unit.
水蒸気改質部２０には、約φ３ｍｍの球状形状を有するＲｕ系の改質触媒が設けられている。具体的には、内筒５と中筒７の側面で構成される空間であって、中筒７の側面部分に、改質触媒の大きさよりも小さな孔径（約φ２ｍｍ）を有するパンチングメタルで構成される棚段１３上に、改質触媒が設置されている。また、変成部２５には、約φ３ｍｍで高さ３ｍｍの円筒形状を有するＣｕ−Ｚｎ系の変成触媒、選択酸化部２６には、約φ３ｍｍの球状形状を有するＲｕ系の選択酸化触媒が設けられている（設置に関する詳細な説明
は、省略する）。
The steam reforming section 20 is provided with a Ru-based reforming catalyst having a spherical shape of about φ3 mm. Specifically, it is a space constituted by the side surfaces of the inner cylinder 5 and the middle cylinder 7, and is constituted by a punching metal having a hole diameter (about φ2 mm) smaller than the size of the reforming catalyst in the side surface portion of the middle cylinder 7. A reforming catalyst is installed on the shelf 13 to be formed. Further, the shift section 25 is provided with a Cu-Zn shift catalyst having a cylindrical shape of approximately 3 mm and a height of 3 mm, and the selective oxidation section 26 is provided with a Ru-based selective oxidation catalyst having a spherical shape of approximately φ3 mm. (Detailed explanation about the installation is omitted).
また、水蒸気改質部２０における改質触媒（あるいは水素含有ガス）の温度（反応温度）を検出する改質温度検出部２１、変成部２５における変成触媒（あるいは原料と水蒸気の混合ガス）の温度を検出する変成温度部２４を備えている。 Further, the temperature of the reforming temperature detection unit 21 for detecting the temperature (reaction temperature) of the reforming catalyst (or hydrogen-containing gas) in the steam reforming unit 20 and the temperature of the shift catalyst (or mixed gas of raw material and steam) in the shift unit 25. Is provided with a metamorphic temperature section 24 for detecting.
また、水素生成装置１は、水蒸気改質部２０における改質反応に必要な反応熱を供給するための加熱部となる、燃焼部２を、内筒５の内側に備えている。燃焼部２は、加熱源となる燃焼ガスを燃焼させるバーナーであり、燃焼部２の燃焼状態を検知するフレームロッドである燃焼検出部２２、及び燃焼部２に燃料用空気を供給する、燃焼空気供給部となる燃焼ファン１８を有している。燃焼部２で燃焼させる燃焼ガスは、燃焼ガス供給経路（図示せず）を介して燃焼部２に供給される。水素生成装置１によって生成された水素含有ガスは、導出部１２を介して、外部に設置される燃料電池等に供給される。なお、フレームロッドは、火炎が形成される時に発生するイオンに電圧を印加し、その時に流れるイオン電流値を測定するデバイスである。また、水蒸気改質部２０と予熱部２３は、燃焼部２で発生させた燃焼排ガスから、燃焼部２との水素生成装置１の壁面を介して供給される構成となっている。また、燃焼排ガスは、図面右上上の排出口から、水素生成装置１の外部へ排気される。 In addition, the hydrogen generator 1 includes a combustion section 2 that is a heating section for supplying reaction heat necessary for the reforming reaction in the steam reforming section 20 inside the inner cylinder 5. The combustion unit 2 is a burner that burns combustion gas that serves as a heating source, a combustion detection unit 22 that is a flame rod that detects the combustion state of the combustion unit 2, and combustion air that supplies fuel air to the combustion unit 2 It has the combustion fan 18 used as a supply part. Combustion gas burned in the combustion unit 2 is supplied to the combustion unit 2 via a combustion gas supply path (not shown). The hydrogen-containing gas generated by the hydrogen generator 1 is supplied to a fuel cell or the like installed outside via the derivation unit 12. The flame rod is a device that applies a voltage to ions generated when a flame is formed and measures the value of the ionic current that flows at that time. Further, the steam reforming unit 20 and the preheating unit 23 are configured to be supplied from the combustion exhaust gas generated in the combustion unit 2 through the wall surface of the hydrogen generator 1 with the combustion unit 2. Further, the combustion exhaust gas is exhausted to the outside of the hydrogen generator 1 from the discharge port at the upper right of the drawing.
予熱部２３は、導出部１２、一酸化炭素低減部（選択酸化部２６、変成部２５）と片側壁面を同一にして、導出部１２、一酸化炭素低減部を流れる水素含有ガス、選択酸化部２６、変成部２５に設けられる触媒と熱交換可能なように構成されている。特に、導出部１２とは、水素生成装置１から導出される水素含有ガスと、水素生成装置１に供給される温度の低い原料及び水とが熱交換される構成となっている。 The preheating unit 23 has the same side wall surface as that of the derivation unit 12 and the carbon monoxide reduction unit (the selective oxidation unit 26 and the conversion unit 25), and the hydrogen-containing gas and the selective oxidation unit flowing through the derivation unit 12 and the carbon monoxide reduction unit. 26, configured to be able to exchange heat with the catalyst provided in the shift unit 25. In particular, the derivation unit 12 is configured to exchange heat between the hydrogen-containing gas derived from the hydrogen generator 1 and the low-temperature raw material and water supplied to the hydrogen generator 1.
水供給経路３には、水供給部が接続されている。原料供給経路４には、原料供給部が接続されている。原料供給経路４から供給される原料は、炭化水素等の少なくとも炭素及び水素元素から構成される有機化合物を含む原料であればよく、例えばメタンを主成分とする都市ガス、天然ガス、ＬＰＧ等である。ここでは、原料の供給源として都市ガスのガスインフララインを用い、そのガスインフララインに、原料中の不臭成分である硫黄化合物を除去する脱硫部が接続されている。例えば脱硫部は、都市ガス中の付臭成分である硫黄化合物を吸着させる、ゼオライト系吸着除去剤を用いることができる。なお、水供給部および原料供給部４は、ブースターポンプを用いることができ、例えば入力する電流パルス、入力電力等を制御することにより、供給する水の流量、原料の流量を調節する機能を有している（詳細は図示せず）。 A water supply unit is connected to the water supply path 3. A raw material supply unit is connected to the raw material supply path 4. The raw material supplied from the raw material supply path 4 may be a raw material containing an organic compound composed of at least carbon and hydrogen elements such as hydrocarbons, for example, city gas mainly composed of methane, natural gas, LPG, etc. is there. Here, a gas infrastructure line of city gas is used as a raw material supply source, and a desulfurization section for removing sulfur compounds, which are odorous components in the raw material, is connected to the gas infrastructure line . For example, the desulfurization part can use a zeolite-based adsorption / removal agent that adsorbs a sulfur compound, which is an odorous component in city gas. The water supply unit and the raw material supply unit 4 can use a booster pump, and have a function of adjusting the flow rate of the supplied water and the flow rate of the raw material, for example, by controlling the input current pulse, input power, and the like. (Details not shown).
なお、図１には示していないが、水素生成装置１には、外筒１５および外筒底板１６に密着するように、セラミックファイバー原綿と結合材を用いて、モールド化された成型断熱材が設けられている。 Although not shown in FIG. 1, the hydrogen generator 1 has a molded heat insulating material molded using ceramic fiber raw cotton and a binding material so as to be in close contact with the outer cylinder 15 and the outer cylinder bottom plate 16. Is provided.
〈水素生成装置１の運転動作〉
次に、水素生成装置１の起動動作、通常時の運転動作、及び停止動作を説明する。
<Operation of the hydrogen generator 1>
Next, the start-up operation, the normal operation operation, and the stop operation of the hydrogen generator 1 will be described.
停止状態から水素生成装置１を起動させる場合、運転制御部（詳細は図示せず）の指令により、原料を燃焼部２に供給し、燃焼部２で原料に着火して水素生成装置１の加熱を開始する。 When starting the hydrogen generator 1 from the stop state, the raw material is supplied to the combustion unit 2 according to a command from an operation control unit (details not shown), and the raw material is ignited by the combustion unit 2 to heat the hydrogen generator 1. To start.
燃焼部２での加熱開始後に、原料供給経路４を通して水素生成装置１（水蒸気改質部２０）に原料を供給するとともに、水供給経路３から水素生成装置１に水を供給し、水と原料との改質反応を開始させる。本実施の形態では、メタンを主成分とする都市ガス（１３
Ａ）を原料とする。水供給部３からの水の供給量は、都市ガスの平均分子式中の炭素原子数１モルに対して水蒸気が３モル程度になるように制御される（スチームカーボン比（Ｓ／Ｃ）で３程度）。
After starting heating in the combustion unit 2, the raw material is supplied to the hydrogen generator 1 (steam reforming unit 20) through the raw material supply path 4, and water is supplied from the water supply path 3 to the hydrogen generator 1. And start the reforming reaction. In the present embodiment, city gas mainly composed of methane (13
A) is used as a raw material. The amount of water supplied from the water supply unit 3 is controlled so that water vapor is about 3 moles per 1 mole of carbon atoms in the average molecular formula of the city gas (steam carbon ratio (S / C) is 3). degree).
水素生成装置１では、水蒸気改質部２０で水蒸気改質反応、変成部２４で変成反応、選択酸化部２６で一酸化炭素の選択酸化反応を進行させる。変成部２４，選択酸化部２６が、反応に適切な温度となり、一酸化炭素濃度を所定濃度（本実施の形態では、ドライガスベースで２０ｐｐｍ以下）まで低減させた後、導出部１２を通して水素含有ガスを、例えば、燃料電池等に供給を開始する。 In the hydrogen generator 1, a steam reforming reaction is performed in the steam reforming unit 20, a shift reaction is performed in the shift unit 24, and a selective oxidation reaction of carbon monoxide is performed in the selective oxidation unit 26. The transformation unit 24 and the selective oxidation unit 26 reach a temperature suitable for the reaction, and after the carbon monoxide concentration is reduced to a predetermined concentration (in this embodiment, 20 ppm or less on a dry gas basis), hydrogen is contained through the derivation unit 12. The supply of gas to, for example, a fuel cell is started.
装置停止時は、原料と水の供給を停止させ、水素生成装置１内の水蒸気改質部２０、変成部２５、選択酸化部２６の各触媒層の温度を低下させる。このとき、燃焼部２の基本動作は停止させる。各触媒層の温度を設定温度まで低下させた後、原料を水素生成装置１に流通させ、ガス経路内部に滞留する水素含有ガスを原料で置換する動作を行い、適宜水素生成装置１を封止する動作を行う。 When the apparatus is stopped, the supply of the raw material and water is stopped, and the temperature of each catalyst layer of the steam reforming unit 20, the shift unit 25, and the selective oxidation unit 26 in the hydrogen generator 1 is lowered. At this time, the basic operation of the combustion unit 2 is stopped. After the temperature of each catalyst layer is lowered to the set temperature, the raw material is circulated through the hydrogen generator 1 and the hydrogen-containing gas staying inside the gas path is replaced with the raw material, and the hydrogen generator 1 is appropriately sealed. To perform the operation.
〈水素生成装置１の構成の特徴〉
水素生成装置１を起動停止させると、その過程で内筒５の側面と中筒７の側面が、熱ひずみにより変形し、改質触媒の一部が圧壊し、触媒表面が削りとられて、粉塵を発生させる。発生した粉塵は、重力により落下して、水素含有ガス流路に堆積する。例えば、相対的に水素含有ガスの通過断面積が小さくなる、中筒の底板に設けられる貫通孔近傍での粉塵の堆積した場合、水素含有ガスの流路を閉塞する可能性がある。
<Characteristics of configuration of hydrogen generator 1>
When the hydrogen generator 1 is started and stopped, the side surface of the inner cylinder 5 and the side surface of the inner cylinder 7 are deformed by thermal strain in the process, a part of the reforming catalyst is crushed, and the catalyst surface is scraped. Generate dust. The generated dust falls by gravity and accumulates in the hydrogen-containing gas flow path. For example, if dust accumulates in the vicinity of the through hole provided in the bottom plate of the middle cylinder, where the passage cross-sectional area of the hydrogen-containing gas becomes relatively small, the flow path of the hydrogen-containing gas may be blocked.
上記課題に対応するため、本実施の形態１の水素生成装置１では、内筒底板６と中筒底板８との間で構成される空間に、中筒底板８に円筒状の突起部１０を設けることで、水素含有ガスの流通に対しての狭隘部１１を構成することを特徴としている。 In order to cope with the above problem, in the hydrogen generator 1 according to the first embodiment, the cylindrical protrusion 10 is formed on the middle cylinder bottom plate 8 in the space formed between the inner cylinder bottom plate 6 and the middle cylinder bottom plate 8. By providing, the narrow part 11 with respect to the distribution | circulation of hydrogen-containing gas is comprised.
上記構成により、水素含有ガスが狭隘部１１を通過する際、比較的大きな粉塵は、狭隘部１１を通過することができず、狭隘部１１近傍で改質触媒の粉塵を捕塵できる。また、突起部１０と、中筒底板８とで、捕塵部１４が構成されることになり、その結果、粉塵が、狭隘部１１から下流側へ流出することを、さらに抑制できることになる。 With the above configuration, when the hydrogen-containing gas passes through the narrow portion 11, relatively large dust cannot pass through the narrow portion 11, and dust of the reforming catalyst can be captured in the vicinity of the narrow portion 11. Moreover, the dust catching part 14 is comprised by the projection part 10 and the middle cylinder bottom plate 8, As a result, it can further suppress that dust flows out from the narrow part 11 to the downstream side.
また、水素生成装置１の水素含有ガスの流れに対する圧力損失を小さくする観点から、狭隘部１１での水素含有ガスの通過断面積が、貫通孔９での水素含有ガスの通過断面積より大きくなるように、突起部１０を設けることが好ましい。 Further, from the viewpoint of reducing the pressure loss with respect to the flow of the hydrogen-containing gas in the hydrogen generator 1, the passage cross-sectional area of the hydrogen-containing gas in the narrow portion 11 is larger than the passage cross-sectional area of the hydrogen-containing gas in the through hole 9. Thus, it is preferable to provide the protrusion 10.
また、粉塵を効果的に捕塵する観点から、狭隘部１１は、本実施の形態１に示すように、中筒底板８の全周方向に連続して設けることが好ましい。 From the viewpoint of effectively collecting dust, the narrow portion 11 is preferably provided continuously in the entire circumferential direction of the middle cylinder bottom plate 8 as shown in the first embodiment.
なお、狭隘部１１は、本実施の形態に示す構成だけでなく、図２〜５に示す狭隘部１１の変形例のような構成としても良い。 In addition, the narrow part 11 is good also as a structure like the modification of not only the structure shown to this Embodiment but the narrow part 11 shown in FIGS.
以下、図２〜５に示す狭隘部１１について説明する。 Hereinafter, the narrow portion 11 shown in FIGS.
図２は、図１の突起部１０の内筒底板６側に、改質触媒が保持されている方向に向けて、円盤状のフランジ部１７を設けた構成として、狭隘部１１を構成した変形例となる。捕塵部１４が、ポケット状に構成されるので、捕塵部１４に捕塵した粉塵が、水素含有ガスの流れ下流側により、移動しにくい構成とすることができる。 FIG. 2 shows a modification in which a narrow portion 11 is formed as a configuration in which a disk-shaped flange portion 17 is provided on the inner cylinder bottom plate 6 side of the projection portion 10 of FIG. 1 in a direction in which the reforming catalyst is held. An example. Since the dust collection part 14 is comprised by pocket shape, it can be set as the structure which the dust trapped in the dust collection part 14 cannot move easily by the flow downstream of a hydrogen containing gas.
図３は、貫通孔９に、突起部となるバーリング部２７を設けた構成として、狭隘部１１
を構成した変形例となる。貫通孔９を構成する際に、バーリング加工することでバーリング部２７を構成することができ、図１に示す突起部１０を設けるより、狭隘部１１を容易に構成することができる。
3 shows a configuration in which a burring portion 27 serving as a protruding portion is provided in the through hole 9, and the narrow portion 11
It becomes the modification which constituted. When the through-hole 9 is configured, the burring portion 27 can be configured by burring, and the narrowed portion 11 can be configured more easily than the projection 10 shown in FIG.
図４は、図３のバーリング部２７の内筒底板６側に、改質触媒が保持されている方向に向けて、円盤状のフランジ部１７を設けた構成として、狭隘部１１を構成した変形例となる。捕塵部１４が、ポケット状に構成されるので、捕塵部１４に捕塵した粉塵が、水素含有ガスの流れ下流側により、移動しにくい構成とすることができる。 FIG. 4 shows a modification in which a narrow portion 11 is formed as a configuration in which a disk-like flange portion 17 is provided on the inner cylinder bottom plate 6 side of the burring portion 27 in FIG. 3 in a direction in which the reforming catalyst is held. An example. Since the dust collection part 14 is comprised by pocket shape, it can be set as the structure which the dust trapped in the dust collection part 14 cannot move easily by the flow downstream of a hydrogen containing gas.
図５は、中筒底板８に、内筒底板６に向けて凸となるようにリブ２８を設け、狭隘部１１を構成した変形例となる。中筒底板８に、リブ２８を設けることで、捕塵効果とともに、中筒底板８の熱変形を抑制する効果を、合わせて発揮できる構成となる。 FIG. 5 shows a modification in which a narrow portion 11 is formed by providing ribs 28 on the middle tube bottom plate 8 so as to protrude toward the inner tube bottom plate 6. By providing the rib 28 in the middle cylinder bottom plate 8, it becomes a structure which can exhibit the effect which suppresses the thermal deformation of the middle cylinder bottom plate 8 with a dust collection effect.
本発明は、起動停止を頻繁に行う、原料と水とを改質反応させ、水素含有ガスを生成させる水素生成装置について有用である。 INDUSTRIAL APPLICABILITY The present invention is useful for a hydrogen generator that frequently starts and stops and causes a reforming reaction between a raw material and water to generate a hydrogen-containing gas.
１ 水素生成装置
２ 燃焼部
３ 水供給経路
４ 原料供給経路
５ 内筒
６ 内筒底板
７ 中筒
８ 中筒底板
９ 貫通孔
１０ 突起部
１１ 狭隘部
１２ 導出部
１３ 棚段
１４ 捕塵部
１５ 外筒
１６ 外筒底板
１７ フランジ部
１８ 燃焼空気供給部
１９ 空気供給経路
２０ 水蒸気改質部
２１ 改質温度検出部
２２ フレームロッド
２３ 予熱部
２４ 変成温度検出部
２５ 変成部
２６ 選択酸化部
２７ バーリング部
２８ リブ
DESCRIPTION OF SYMBOLS 1 Hydrogen generator 2 Combustion part 3 Water supply path 4 Raw material supply path 5 Inner cylinder 6 Inner cylinder bottom plate 7 Middle cylinder 8 Middle cylinder bottom plate 9 Through-hole 10 Protrusion part 11 Narrow part 12 Lead-out part 13 Shelf stage 14 Dust collection part 15 Outside Tube 16 Outer tube bottom plate 17 Flange portion 18 Combustion air supply portion 19 Air supply path 20 Steam reforming portion 21 Reforming temperature detection portion 22 Frame rod 23 Preheating portion 24 Transformation temperature detection portion 25 Transformation portion 26 Selective oxidation portion 27 Burling portion 28 rib
Claims (12)
貫通孔が設けられる底板を備え、前記内筒の外側に配される中筒と、
底板を備え、前記中筒の外側に配される外筒と、
少なくとも前記内筒と前記中筒との間で構成される空間に、原料と水蒸気とを改質反応させ水素含有ガスを生成させる改質触媒が保持されており、
前記改質触媒の粉塵が、重力により前記内筒の底板と前記中筒の底板との間で構成される空間に落下する水素生成装置であって、
前記内筒の底板と前記中筒の底板との間で構成される空間に、前記水素含有ガスの流路となる前記貫通孔よりも前記水素含有ガスの上流側で前記粉塵を捕塵する捕塵部を設けた水素生成装置。 An inner cylinder with a bottom plate;
Comprising a bottom plate provided with a through-hole, and a middle cylinder disposed outside the inner cylinder;
An outer cylinder that includes a bottom plate and is arranged outside the middle cylinder;
At least in a space formed between the inner cylinder and the middle cylinder, a reforming catalyst that generates a hydrogen-containing gas by reforming a raw material and water vapor is held.
The hydrogen generating device in which dust of the reforming catalyst falls into a space formed between the bottom plate of the inner cylinder and the bottom plate of the middle cylinder by gravity,
The space comprised between the bottom plate in said cylinder and a bottom plate of the inner cylinder, than the through-hole serving as a flow path of the hydrogen-containing gas capturing for dust trapping the dust in the upstream side of the hydrogen-containing gas A hydrogen generator with a dust part .
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| US6258330B1 (en) * | 1998-11-10 | 2001-07-10 | International Fuel Cells, Llc | Inhibition of carbon deposition on fuel gas steam reformer walls |
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