JP2003183003A - Multi-tube reactor - Google Patents
Multi-tube reactorInfo
- Publication number
- JP2003183003A JP2003183003A JP2001379876A JP2001379876A JP2003183003A JP 2003183003 A JP2003183003 A JP 2003183003A JP 2001379876 A JP2001379876 A JP 2001379876A JP 2001379876 A JP2001379876 A JP 2001379876A JP 2003183003 A JP2003183003 A JP 2003183003A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction tube
- reactor
- reaction
- tube
- 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.)
- Pending
Links
- 238000006243 chemical reaction Methods 0.000 claims abstract description 115
- 239000003054 catalyst Substances 0.000 claims abstract description 92
- 230000007423 decrease Effects 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 18
- 239000008187 granular material Substances 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 239000000446 fuel Substances 0.000 abstract description 28
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 abstract description 6
- 238000012856 packing Methods 0.000 abstract 3
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002737 fuel gas Substances 0.000 description 28
- 239000000567 combustion gas Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000006866 deterioration Effects 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、燃料電池システム
の改質器等に用いられる多管式反応器に関する。TECHNICAL FIELD The present invention relates to a multitubular reactor used for a reformer or the like of a fuel cell system.
【０００２】[0002]
【従来の技術】多管式反応器は、例えば燃料電池システ
ムにおける燃料改質装置の改質器として使用されてい
る。この改質器としての多管式反応器は、従来例えば図
５に示すように改質用触媒Ａを充填した複数の反応管
（改質管）Ｂと、触媒Ａに反応熱を与える燃焼器Ｃと、
この燃焼器Ｃの高温燃焼ガスを導く燃焼筒Ｄとを備えて
いる（特開平７−３３４０２）。2. Description of the Related Art A multi-tube reactor is used, for example, as a reformer of a fuel reformer in a fuel cell system. This multi-tube reactor as a reformer is conventionally composed of a plurality of reaction tubes (reforming tubes) B filled with a reforming catalyst A as shown in FIG. 5, and a combustor for giving reaction heat to the catalyst A. C,
A combustion cylinder D for guiding the high temperature combustion gas of the combustor C is provided (JP-A-7-33402).
【０００３】この場合、燃焼筒Ｄ内に設けたガイドフィ
ンＥによって高熱燃焼ガスをスパイラル流にして上昇さ
せ、容器内の上部に設けた整流板Ｆで高熱燃焼ガスを半
径方向に均一に分散させて複数の反応管Ｂの頂部よりダ
ウンフローさせる。これにより、各反応管Ｂを加熱して
触媒Ａに反応熱を付与する。改質すべき炭化水素系燃料
は、入口ノズルＧから各反応管Ｂに導入されると共に、
反応管Ｂの触媒Ａ中を上昇しながら通過し、触媒Ａの作
用によって水素を主体とした燃料ガスに改質される。改
質された燃料ガスは反応管Ｂの内部に設けられたガス管
Ｈ内を通って下降し、出口ノズルＩから取り出される。
燃焼ガスは、排出口Ｊから排出される。In this case, the guide fins E provided in the combustion cylinder D raise the high-heated combustion gas into a spiral flow and raise it, and the straightening plate F provided in the upper portion of the container uniformly disperses the high-heated combustion gas in the radial direction. Down flow from the tops of the plurality of reaction tubes B. Thereby, each reaction tube B is heated and reaction heat is given to the catalyst A. The hydrocarbon fuel to be reformed is introduced into each reaction tube B from the inlet nozzle G, and
As it passes through the catalyst A in the reaction tube B while rising, it is reformed into a fuel gas mainly containing hydrogen by the action of the catalyst A. The reformed fuel gas descends through the gas pipe H provided inside the reaction tube B and is taken out from the outlet nozzle I.
The combustion gas is discharged from the discharge port J.
【０００４】取り出された燃料ガスは、通常ＣＯ変成器
及びＣＯ除去器を経て燃料ガス中の一酸化炭素が所定濃
度となるように変成され、燃料電池のアノード（燃料
極）に供給される。一方、燃料電池のカソード（空気
極）には空気が供給され、電解質を介して電気化学反応
が生じることにより電気と水とが生成される。The taken-out fuel gas is usually passed through a CO shift converter and a CO remover to be transformed so that carbon monoxide in the fuel gas has a predetermined concentration and supplied to the anode (fuel electrode) of the fuel cell. On the other hand, air is supplied to the cathode (air electrode) of the fuel cell, and an electrochemical reaction occurs via the electrolyte to generate electricity and water.
【０００５】[0005]
【発明が解決しようとする課題】上記した従来の多管式
反応器によると、複数の反応管Ｂをそれぞれ周囲均一に
加熱することができるので熱応力の差による反応管Ｂの
変形を防止し、且つ反応管内の触媒Ａに均等に反応熱を
付与できるので触媒利用率の向上が図れる。しかしなが
ら、この多管式反応器では、各反応管の最上部に触媒充
填部がなく空隙となっている。この場合、反応器の運転
に伴う繰り返しの熱サイクルにより反応管Ｂが熱膨張、
収縮を起こす。この時、内部に充填されている触媒Ａが
圧壊等により粉化し、各反応管Ｂの触媒充填体積が減少
し触媒充填量に差が生じる。このため、各反応管Ｂで触
媒層に圧力差が発生し、各反応管Ｂへのガス分配が不均
一になる。又、各反応管Ｂでの触媒層に温度差が生じ、
反応器の性能低下や寿命の低下が発生するという問題が
あった。According to the above-mentioned conventional multi-tubular reactor, the plurality of reaction tubes B can be uniformly heated in their surroundings, so that the reaction tubes B are prevented from being deformed due to the difference in thermal stress. In addition, since the reaction heat can be evenly applied to the catalyst A in the reaction tube, the catalyst utilization rate can be improved. However, in this multi-tubular reactor, there is no catalyst filling portion at the top of each reaction tube, and there is a void. In this case, the reaction tube B undergoes thermal expansion due to repeated thermal cycles associated with the operation of the reactor,
Cause contraction. At this time, the catalyst A filled inside is pulverized by crushing or the like, and the catalyst filling volume of each reaction tube B is reduced, resulting in a difference in the catalyst filling amount. Therefore, a pressure difference is generated in the catalyst layer in each reaction tube B, and gas distribution to each reaction tube B becomes uneven. Further, a temperature difference occurs in the catalyst layer in each reaction tube B,
There was a problem that the performance of the reactor and the life of the reactor were reduced.
【０００６】そこで、本発明はこのような問題を解消す
るためになされ、熱サイクルにより各反応管の触媒充填
体積が減少し、充填量が減少しても各反応管の体積減少
分を補えるようにした多管式反応器を提供することを目
的とする。Therefore, the present invention has been made to solve such a problem, and the catalyst filling volume of each reaction tube is reduced by the heat cycle, and even if the filling amount is reduced, the volume reduction amount of each reaction tube can be compensated. An object of the present invention is to provide a multi-tubular reactor having the above structure.
【０００７】[0007]
【課題を解決するための手段】この目的を達成するため
の手段として、本発明は、請求項１のように、触媒を充
填した複数の反応管が立設状態で内蔵された多管式反応
器において、この反応器の上部に空間層を設け、この空
間層と各反応管の上部を連通させると共に、空間層に充
填補助物を充填したことを特徴とする多管式反応器を要
旨する。又、請求項２のように、前記充填補助物は反応
管に充填した触媒と同じ触媒であること、請求項３のよ
うに、前記充填補助物は反応管に充填した触媒とほぼ同
大の粒状物であること、請求項４のように、前記充填補
助物は反応管に充填した触媒が粉化等により体積減少し
た場合に、反応管に落ち込んで体積減少分を補うこと、
を特徴とするものである。As a means for attaining this object, the present invention provides a multi-tube reaction in which a plurality of reaction tubes filled with a catalyst are installed in an upright state as in claim 1. In the reactor, a multi-tube reactor characterized in that a space layer is provided on the upper part of the reactor, the space layer is connected to the upper part of each reaction tube, and the space layer is filled with a filling auxiliary material . Further, as in claim 2, the auxiliary filling material is the same catalyst as the catalyst filled in the reaction tube. As in claim 3, the auxiliary filling material has substantially the same size as the catalyst filled in the reaction tube. It is a granular material, and when the volume of the catalyst filled in the reaction tube is reduced due to pulverization or the like, the filling auxiliary substance falls into the reaction tube to compensate for the volume reduction,
It is characterized by.
【０００８】本発明では、多管式反応器の上部に各反応
管の上部に連通する空間層を設け、この空間層に触媒と
同一の触媒又は触媒とほぼ同大の粒状物等の充填補助物
を充填したので、熱サイクルにより各反応管の触媒充填
体積が減少し、充填量が減少しても充填補助物によって
各反応管の体積減少分を補うことができる。このため、
各反応管での充填体積に変化が生じることがなく、ガス
分配を均一に行うことができる。In the present invention, a space layer communicating with the upper part of each reaction tube is provided in the upper part of the multi-tube reactor, and the space layer is filled with the same catalyst as the catalyst or a granular material having the same size as the catalyst. Since the material is charged, the catalyst filling volume of each reaction tube is reduced by the heat cycle, and even if the filling amount is reduced, the volume reduction of each reaction tube can be compensated by the auxiliary filling material. For this reason,
It is possible to uniformly distribute the gas without changing the filling volume in each reaction tube.
【０００９】[0009]
【発明の実施の形態】次に、本発明に係る多管式反応器
の実施形態を添付図面に基づいて説明する。図１は、本
発明に係る多管式反応器を改質器に適用した実施形態を
示すもので、（ａ）は概略縦断面図、（ｂ）はそのＸ−
Ｘ線断面図である。BEST MODE FOR CARRYING OUT THE INVENTION Next, an embodiment of a multitubular reactor according to the present invention will be described with reference to the accompanying drawings. FIG. 1 shows an embodiment in which the multitubular reactor according to the present invention is applied to a reformer. (A) is a schematic vertical sectional view, and (b) is its X-.
It is an X-ray sectional view.
【００１０】図１（ａ）、（ｂ）において、１は円筒状
の反応器（改質器）であり、その内部に複数の反応管２
が円周方向に一定の間隔をあけて立設され、各反応管２
の下端部は原燃料室３に連結され、上端部は上部に設け
られた空間層４（空間室）に連結されて連通している。In FIGS. 1 (a) and 1 (b), 1 is a cylindrical reactor (reformer) in which a plurality of reaction tubes 2 are provided.
Are erected at regular intervals in the circumferential direction, and each reaction tube 2
The lower end portion of is connected to the raw fuel chamber 3, and the upper end portion thereof is connected to and communicates with the space layer 4 (space chamber) provided in the upper portion.
【００１１】各反応管２の内部には改質用の触媒５が充
填され、その粒状の触媒５を保持するために各反応管２
の下端部には金網２ａが取り付けられている。触媒５は
各反応管２の上端まで充填されている。The inside of each reaction tube 2 is filled with a reforming catalyst 5, and each reaction tube 2 holds the granular catalyst 5.
A wire mesh 2a is attached to the lower end of the. The catalyst 5 is filled up to the upper end of each reaction tube 2.
【００１２】前記空間層４の内部には、充填補助物６が
各反応管２の触媒５から連続して充填されている。この
充填補助物６は、触媒５と同一の触媒又は触媒５とほぼ
同じ大きさの粒状物であることが好ましい。粒状物とし
ては、例えばアルミナボールを用いることができ、その
他ジルコニアやＳＵＳ等で形成したものを使用できる。A filling auxiliary material 6 is continuously filled from the catalyst 5 of each reaction tube 2 into the space layer 4. The auxiliary filling material 6 is preferably the same catalyst as the catalyst 5 or a granular material having substantially the same size as the catalyst 5. As the granular material, for example, alumina balls can be used, and those formed of zirconia, SUS, or the like can be used.
【００１３】反応器１の下部にはバーナ７が設置され、
このバーナ７で燃焼された高熱燃焼ガスは前記原燃料室
３の中央部に設けられた燃焼ガス通路８を通って反応器
１内に入り、上昇しながら複数の反応管２を加熱すると
共に、反応器１の側壁上部に取り付けられた排出口１ａ
から排出する。A burner 7 is installed at the bottom of the reactor 1,
The high-temperature combustion gas combusted by the burner 7 enters the reactor 1 through the combustion gas passage 8 provided at the center of the raw fuel chamber 3 and heats the reaction tubes 2 while rising. Discharge port 1a mounted on the upper side wall of the reactor 1
Discharge from.
【００１４】又、反応器１の側壁下部には、原燃料室３
に通じる燃料ガス導入口１ｂが取り付けられ、側壁上端
部には空間層４に通じる燃料ガス取出口１ｃが取り付け
られている。In the lower part of the side wall of the reactor 1, the raw fuel chamber 3
A fuel gas inlet 1b leading to the space layer 4 is attached, and a fuel gas outlet 1c leading to the space layer 4 is attached to the upper end of the side wall.
【００１５】このように構成された多管式反応器（改質
器）において、原燃料ガス（都市ガス等）がバーナ７に
供給されて燃焼し、その高熱燃焼ガスは前記のように原
燃料室３中央部の燃焼ガス通路８を通った後各反応管２
の周囲に流入し、複数の反応管２を加熱する。これによ
り、各反応管２の触媒５が反応温度（通常６５０℃〜７
００℃）まで昇温される。In the thus constructed multi-tube reactor (reformer), the raw fuel gas (city gas or the like) is supplied to the burner 7 and burned, and the high-heat combustion gas is the raw fuel as described above. After passing through the combustion gas passage 8 in the center of the chamber 3, each reaction tube 2
To heat the plurality of reaction tubes 2. As a result, the catalyst 5 in each reaction tube 2 is heated to the reaction temperature (usually 650 ° C to 7
The temperature is raised to 00 ° C.
【００１６】改質すべき原燃料ガスは蒸気が混入され
て、前記燃料ガス導入口１ｂから原燃料室３に供給さ
れ、この原燃料室３から各反応管２に分配される。各反
応管２に流入した原燃料ガスは、触媒５層を通過しなが
ら上昇し、その際触媒５の作用によって水蒸気改質（Ｃ
Ｈ４＋Ｈ２Ｏ→ＣＯ＋３Ｈ２）される。The raw fuel gas to be reformed is mixed with steam, supplied to the raw fuel chamber 3 through the fuel gas inlet 1b, and distributed from the raw fuel chamber 3 to each reaction tube 2. The raw fuel gas flowing into each reaction tube 2 rises while passing through the catalyst 5 layer, and at that time, the action of the catalyst 5 causes steam reforming (C
H 4 + H 2 O → CO + 3H 2 ).
【００１７】これにより、原燃料ガスは水素主体の燃料
ガスに改質され、各反応管２の上端から前記充填補助物
６を通過して空間層４に流入し、燃料ガス取出口１ｃか
ら取り出される。As a result, the raw fuel gas is reformed into a hydrogen-based fuel gas, passes through the filling aids 6 from the upper ends of the reaction tubes 2 and flows into the space layer 4, and is taken out from the fuel gas outlet 1c. Be done.
【００１８】反応器１の運転中は、繰り返しの熱サイク
ルにより反応管２が熱膨張、収縮を起こす。この時、内
部に充填されている触媒５が圧壊等により粉化し、各反
応管２の触媒充填体積が減少し触媒充填量に差が生じ
る。During operation of the reactor 1, the reaction tube 2 undergoes thermal expansion and contraction due to repeated thermal cycles. At this time, the catalyst 5 filled inside is pulverized by crushing or the like, and the volume of catalyst filled in each reaction tube 2 is reduced, resulting in a difference in the amount of catalyst filled.
【００１９】反応管２内の触媒５の体積が減少すると、
前記充填補助物６が反応管２内に落ち込んでその減少分
を補填する。これにより、各反応管２の触媒充填量に差
が生じることがなく、原燃料室３からの各反応管２への
ガス分配が均一になる。又、各反応管２での触媒５に温
度差が生じることなく、反応器１の性能低下や寿命の低
下を防ぐことができる。充填補助物６が触媒５と同一の
触媒である場合には、各反応管２内の触媒レベルを常時
一定に保持することができる。粉化した触媒はやがて原
燃料室３に落下するので、反応管２が目詰まりすること
はない。When the volume of the catalyst 5 in the reaction tube 2 decreases,
The auxiliary filling material 6 falls into the reaction tube 2 and compensates for the decrease. As a result, there is no difference in the catalyst filling amount of each reaction tube 2, and the gas distribution from the raw fuel chamber 3 to each reaction tube 2 becomes uniform. Further, there is no difference in temperature between the catalysts 5 in the reaction tubes 2, and it is possible to prevent deterioration of the performance and life of the reactor 1. When the auxiliary filling material 6 is the same catalyst as the catalyst 5, the catalyst level in each reaction tube 2 can always be kept constant. Since the pulverized catalyst eventually falls into the raw fuel chamber 3, the reaction tube 2 is not clogged.
【００２０】空間層４内の充填補助物６の高さは、反応
管２の全長の５％以上であることが好ましい。５％未満
であると、長時間運転した場合に充填補助物６が不足
し、各反応管２の充填体積に変化が現れる。その結果、
各反応管２へのガス分配に差が生じ、触媒層に温度分布
のむらができる。本実施形態では、充填補助物６の高さ
を反応管２の全長の１０％とした。The height of the auxiliary filling material 6 in the space layer 4 is preferably 5% or more of the total length of the reaction tube 2. If it is less than 5%, the auxiliary filling material 6 will be insufficient and the filling volume of each reaction tube 2 will change when operating for a long time. as a result,
A difference occurs in gas distribution to each reaction tube 2, and the temperature distribution in the catalyst layer becomes uneven. In this embodiment, the height of the auxiliary filling material 6 is 10% of the total length of the reaction tube 2.
【００２１】運転時間３０００時間（３９０サイクル）
後には、各反応管２の触媒体積は粉化等により減少し、
触媒量は減少するものの、空間層４に存在する充填補助
物６が自然に落ち込むことで空隙部を生じさせない。こ
のため、各反応管２の差圧が小さく、各反応管２へガス
流量を長期間に亘って均一に流すことが可能となった。Operating time 3000 hours (390 cycles)
Later, the catalyst volume of each reaction tube 2 decreases due to pulverization,
Although the amount of the catalyst is reduced, the filling auxiliary substance 6 existing in the space layer 4 naturally falls and does not generate a void. Therefore, the differential pressure between the reaction tubes 2 is small, and the gas flow rate can be made to flow uniformly to each reaction tube 2 for a long period of time.
【００２２】図２は、各反応管２の触媒層温度分布を測
定したグラフであり、この場合は５本の反応管に番号
〜を付けて区別してある。反応管〜反応管の触媒
層温度はほぼ６８０℃〜７１０℃の範囲内に収まり、各
反応管２の触媒層温度差は約３０℃に改善された。ちな
みに、従来例では各反応管の触媒層温度はほぼ６２０℃
〜６８０℃の範囲内であり、約６０℃の温度差が生じて
いた。従来例に比して触媒層温度のばらつきが極めて小
さいことが判明した。FIG. 2 is a graph in which the temperature distribution of the catalyst layer in each reaction tube 2 is measured. In this case, the five reaction tubes are numbered to distinguish them. The temperature of the catalyst layer between the reaction tube and the reaction tube was within the range of approximately 680 ° C. to 710 ° C., and the temperature difference of the catalyst layer between the reaction tubes 2 was improved to approximately 30 ° C. By the way, in the conventional example, the temperature of the catalyst layer of each reaction tube is about 620 ° C.
It was in the range of ˜680 ° C., and a temperature difference of about 60 ° C. occurred. It was found that the variation in the catalyst layer temperature was extremely small compared to the conventional example.
【００２３】図３は、本発明に係る多管式反応器をＣＯ
除去器に適用した実施形態を示すもので、（ａ）は概略
縦断面図、（ｂ）はそのＸ−Ｘ線断面図である。前記反
応器１（改質器）で改質された燃料ガス中には、ＣＯが
１０数％含まれており、この燃料ガスをそのまま燃料電
池（図略）に供給すると、電極触媒を被毒して電池性能
が低下する。このため、反応器１からの燃料ガスをＣＯ
変成器（図略）に送り込んで、ＣＯをＣＯ２に変成する
（ＣＯ＋Ｈ２Ｏ→ＣＯ２＋Ｈ２）。これにより、燃料ガ
ス中のＣＯ濃度を１％以下に低下するが、更にこの燃料
ガスをＣＯ除去器に送り込んでＣＯを選択的に酸化し、
ＣＯ濃度を１０ｐｐｍ以下に低減してから燃料電池に供
給することが行われている。FIG. 3 shows a multitubular reactor according to the present invention with CO
The embodiment applied to a remover is shown, (a) is a schematic longitudinal sectional view, and (b) is its XX line sectional view. The fuel gas reformed in the reactor 1 (reformer) contains 10% or more of CO. If this fuel gas is directly supplied to the fuel cell (not shown), the electrode catalyst is poisoned. The battery performance will be reduced. Therefore, the fuel gas from the reactor 1 is CO
It is sent to a transformer (not shown) to transform CO into CO 2 (CO + H 2 O → CO 2 + H 2 ). As a result, the CO concentration in the fuel gas is reduced to 1% or less, but the fuel gas is further sent to the CO remover to selectively oxidize CO,
The CO concentration is reduced to 10 ppm or less and then supplied to the fuel cell.
【００２４】図３（ａ）、（ｂ）において、１１は円筒
状の反応器（ＣＯ除去器）であり、その内部に複数の反
応管１２が円周方向に一定の間隔をあけて立設され、各
反応管１２の下端部はリング状の燃料室１３に連結さ
れ、上端部は空間層１４（空間室）に連結されて連通し
ている。In FIGS. 3 (a) and 3 (b), 11 is a cylindrical reactor (CO remover), in which a plurality of reaction tubes 12 are erected at regular intervals in the circumferential direction. The lower end of each reaction tube 12 is connected to the ring-shaped fuel chamber 13, and the upper end is connected to and communicates with the space layer 14 (space chamber).
【００２５】各反応管１２の内部には選択酸化用の触媒
１５が充填され、その粒状の触媒１５を保持するために
各反応管１２の下端部には金網１２ａが取り付けられて
いる。触媒１５は各反応管１２の上端まで充填されてい
る。A catalyst 15 for selective oxidation is filled in each reaction tube 12, and a wire mesh 12a is attached to the lower end of each reaction tube 12 to hold the granular catalyst 15. The catalyst 15 is filled up to the upper end of each reaction tube 12.
【００２６】前記空間層１４の内部には、各反応管１２
と同一の触媒１６が各反応管１２の触媒１５から連続し
て充填され、反応管１２の全長とほぼ同等の高さとし
た。Inside the space layer 14, each reaction tube 12 is provided.
The same catalyst 16 as above was continuously filled from the catalyst 15 of each reaction tube 12 to have a height almost equal to the entire length of the reaction tube 12.
【００２７】燃料室１３の側壁下部には燃料ガス導入口
１３ａが取り付けられ、反応器１１の側壁を貫通して外
部に突出しており、又空間層１４の側壁上部には燃料ガ
ス取出口１４ａが取り付けられ、この燃料ガス取出口１
４ａも反応器１１の側壁を貫通して外部に突出してい
る。A fuel gas inlet 13a is attached to the lower portion of the side wall of the fuel chamber 13, penetrates the side wall of the reactor 11 and protrudes to the outside, and a fuel gas outlet 14a is provided above the side wall of the space layer 14. Installed, this fuel gas outlet 1
4a also penetrates the side wall of the reactor 11 and projects to the outside.
【００２８】燃料室１３及び空間層１４の外壁と、反応
器１１の内壁との間は隙間があって通気路１７になって
おり、反応器１１の下部に設けられた入口１１ａから供
給される冷却空気が、通気路１７及び燃料室１３の中央
部に設けられた冷気通路１８を通って反応器１１の上部
に設けられた出口１１ｂから排出される。ここでの触媒
反応は、改質器とは異なって発熱反応であるため、反応
温度以上に昇温しないように各反応管１２を冷却する必
要がある。There is a gap between the outer walls of the fuel chamber 13 and the space layer 14 and the inner wall of the reactor 11 to form a ventilation path 17, which is supplied from an inlet 11a provided at the bottom of the reactor 11. The cooling air is discharged from the outlet 11b provided at the upper portion of the reactor 11 through the ventilation passage 17 and the cold air passage 18 provided at the center of the fuel chamber 13. Since the catalytic reaction here is an exothermic reaction unlike the reformer, it is necessary to cool each reaction tube 12 so as not to raise the temperature above the reaction temperature.
【００２９】選択酸化すべき燃料ガスは空気が混入され
て、前記燃料ガス導入口１３ａから燃料室１３に供給さ
れ、この燃料室１３から各反応管１２に分配される。各
反応管１２に流入した燃料ガスは、触媒１５層を通過し
ながら上昇し、その際触媒１５の作用によって選択酸化
される（ＣＯ＋１／２Ｏ２→ＣＯ２）。The fuel gas to be selectively oxidized is mixed with air, supplied from the fuel gas inlet 13a to the fuel chamber 13, and is distributed from the fuel chamber 13 to each reaction tube 12. The fuel gas flowing into each reaction tube 12 rises while passing through the catalyst 15 layer, and at that time, is selectively oxidized by the action of the catalyst 15 (CO + 1 / 2O 2 → CO 2 ).
【００３０】これにより、燃料ガス中のＣＯは所定濃度
に低減され、各反応管１２の上端から前記充填補助物１
６を通過して空間層１４に流入し、燃料ガス取出口１４
ａから取り出される。取り出された燃料ガスは、燃料電
池に供給される。As a result, CO in the fuel gas is reduced to a predetermined concentration, and the auxiliary filling material 1 is supplied from the upper end of each reaction tube 12.
6 and flows into the space layer 14, and the fuel gas outlet 14
taken out from a. The taken out fuel gas is supplied to the fuel cell.
【００３１】本実施形態において、運転時間５０００時
間（４８０サイクル）後には、各反応管１２の触媒体積
は粉化等により減少し、触媒量は減少するが前記充填補
助物１６が反応管１２内に落ち込んでその減少分を補え
る。これにより、各反応管１２の触媒充填量に差が生じ
ることがなく、燃料室１３からの各反応管１２へのガス
分配が均一になる。又、各反応管１２での触媒１５に温
度差が生じることなく、反応器１１の性能低下や寿命の
低下を防ぐことができる。充填補助物１６は触媒１５と
同一の触媒であるから、各反応管１２内の触媒レベルを
常時一定に保持することができる。In the present embodiment, after 5000 hours of operation (480 cycles), the catalyst volume of each reaction tube 12 decreases due to pulverization or the like, and the amount of catalyst decreases, but the auxiliary filling material 16 remains inside the reaction tube 12. To compensate for the decrease. As a result, there is no difference in the catalyst filling amount of each reaction tube 12, and the gas distribution from the fuel chamber 13 to each reaction tube 12 becomes uniform. Further, there is no temperature difference in the catalyst 15 in each reaction tube 12, and it is possible to prevent performance deterioration and life shortening of the reactor 11. Since the auxiliary filling material 16 is the same catalyst as the catalyst 15, the catalyst level in each reaction tube 12 can always be kept constant.
【００３２】図４は、各反応管１２の触媒層温度分布を
測定したグラフであり、この場合は４本の反応管に番号
〜を付けて区別してある。反応管〜反応管の触
媒層温度は、ほぼ１４５℃〜１６０℃の範囲内に収ま
り、各反応管１２の触媒層温度差は約１５℃に改善され
た。従来例では各反応管の触媒層温度はほぼ１２０℃〜
１８０℃の範囲内であり、約６０℃の温度差が生じてい
た。従来例に比して触媒層温度のばらつきが極めて小さ
いことが判明した。FIG. 4 is a graph in which the temperature distribution of the catalyst layer in each reaction tube 12 is measured. In this case, four reaction tubes are numbered to distinguish them. The temperature of the catalyst layer between the reaction tube and the reaction tube was within the range of approximately 145 ° C. to 160 ° C., and the difference in the catalyst layer temperature of each reaction tube 12 was improved to about 15 ° C. In the conventional example, the temperature of the catalyst layer of each reaction tube is approximately 120 ° C.
It was in the range of 180 ° C., and a temperature difference of about 60 ° C. occurred. It was found that the variation in the catalyst layer temperature was extremely small compared to the conventional example.
【００３３】反応器出口でのＣＯ濃度は、従来は２０ｐ
ｐｍまで上昇するが、本実施形態では１０ｐｐｍ以下と
低濃度を維持している。又、本発明をＣＯ除去器に適用
した場合、ＣＯ選択酸化で発生する発熱部（特に上流部
で発熱が大きい）を多管式にすることにより伝熱面積が
増加し、空冷でも効率良く冷却を行うことが可能にな
り、システムのシンプル化が図れる。The CO concentration at the reactor outlet is conventionally 20 p
Although it rises to pm, in the present embodiment, the low concentration of 10 ppm or less is maintained. Further, when the present invention is applied to a CO remover, the heat transfer area generated by CO selective oxidation (especially the heat generation is large in the upstream part) is increased by a multi-tube type to increase the heat transfer area and efficiently cool even by air cooling. Can be performed, and the system can be simplified.
【００３４】尚、上記実施形態では改質器又はＣＯ除去
器に適用した例で説明したが、本発明の反応器は、触媒
作用により燃料ガス中のＣＯを変成するＣＯ変成器にも
充分適用することが可能である。Although the above embodiment has been described with reference to an example applied to a reformer or a CO remover, the reactor of the present invention is also sufficiently applied to a CO shifter that shifts CO in fuel gas by a catalytic action. It is possible to
【００３５】[0035]
【発明の効果】以上説明したように、本発明は、複数の
反応管に触媒を充填した多管式反応器において、運転に
伴う熱サイクルにより触媒が圧壊して粉化し、各反応管
の触媒充填体積が減少し、充填量が減少しても各反応管
の上部に連通する空間層に収納した充填補助物により各
反応管の体積減少分を補うことができる。これにより、
各反応管４の触媒充填量に差が生じることがなく、各反
応管４へのガス分配が長期間に亘って均一になり、又各
反応管４での触媒７に温度差が生じることなく、反応器
の性能低下や寿命の低下を防ぐことができる等の優れた
効果が得られる。As described above, according to the present invention, in a multi-tube reactor in which a plurality of reaction tubes are filled with a catalyst, the catalyst is crushed and pulverized due to the thermal cycle accompanying the operation, and the catalyst of each reaction tube is Even if the filling volume is reduced and the filling amount is reduced, the volume reduction amount of each reaction tube can be compensated by the auxiliary filling material contained in the space layer communicating with the upper portion of each reaction tube. This allows
There is no difference in the catalyst filling amount of each reaction tube 4, the gas distribution to each reaction tube 4 is uniform over a long period, and there is no temperature difference in the catalyst 7 in each reaction tube 4. Further, it is possible to obtain excellent effects such as prevention of performance deterioration and life reduction of the reactor.
【図１】本発明に係る多管式反応器を改質器に適用した
実施形態を示すもので、（ａ）は概略縦断面図、（ｂ）
はそのＸ−Ｘ線断面図である。FIG. 1 shows an embodiment in which a multi-tube reactor according to the present invention is applied to a reformer, in which (a) is a schematic vertical sectional view, and (b).
Is a sectional view taken along line XX.
【図２】各反応管の触媒層温度分布を測定したグラフ図FIG. 2 is a graph showing the temperature distribution of the catalyst layer in each reaction tube.
【図３】本発明に係る多管式反応器をＣＯ除去器に適用
した実施形態を示すもので、（ａ）は概略縦断面図、
（ｂ）はそのＸ−Ｘ線断面図である。FIG. 3 shows an embodiment in which the multitubular reactor according to the present invention is applied to a CO remover, (a) is a schematic vertical sectional view,
(B) is the XX sectional view.
【図４】各反応管の触媒層温度分布を測定したグラフ図FIG. 4 is a graph showing the temperature distribution of the catalyst layer in each reaction tube.
【図５】従来の多管式反応器の一例を示す説明図FIG. 5 is an explanatory view showing an example of a conventional multitubular reactor.
１…反応器（改質器） ２…反応管 ３…原燃料室 ４…空間層（空間室） ５…触媒 ６…充填補助物 ７…バーナ ８…燃焼ガス通路 １１…反応器（ＣＯ除去器） １２…反応管 １３…燃料室 １４…空間層（空間室） １５…触媒 １６…充填補助物 １７…通気路 １８…冷気通路 1 ... Reactor (reformer) 2 ... Reaction tube 3 ... Raw fuel chamber 4 ... Space layer (space room) 5 ... Catalyst 6 ... filling aid 7 ... Burner 8 ... Combustion gas passage 11 ... Reactor (CO remover) 12 ... Reaction tube 13 ... Fuel chamber 14 ... Space layer (space room) 15 ... Catalyst 16 ... Filling aid 17 ... Ventilation path 18 ... Cold aisle
───────────────────────────────────────────────────── フロントページの続き (72)発明者 門脇 正天 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 秋山 幸徳 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 Ｆターム(参考） 4G040 EA03 EA06 EB14 EB23 4G070 AA01 AB04 BB03 CA01 CA07 DA15 5H027 AA02 BA01 BA16 BA17 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor, Masanori Kadowaki 2-5-3 Keihan Hondori, Moriguchi City, Osaka Prefecture Within Yo Denki Co., Ltd. (72) Inventor Yukinori Akiyama 2-5-3 Keihan Hondori, Moriguchi City, Osaka Prefecture Within Yo Denki Co., Ltd. F-term (reference) 4G040 EA03 EA06 EB14 EB23 4G070 AA01 AB04 BB03 CA01 CA07 DA15 5H027 AA02 BA01 BA16 BA17
Claims (4)
内蔵された多管式反応器において、この反応器の上部に
空間層を設け、この空間層と各反応管の上部を連通させ
ると共に、空間層に充填補助物を充填したことを特徴と
する多管式反応器。1. A multi-tube reactor in which a plurality of reaction tubes filled with a catalyst are installed in an upright state, and a space layer is provided above the reactor, and the space layer is communicated with the upper part of each reaction tube. A multi-tubular reactor characterized in that the space layer is filled with a filling aid.
と同じ触媒である請求項１記載の多管式反応器。2. The multitubular reactor according to claim 1, wherein the auxiliary filling material is the same catalyst as the catalyst filled in the reaction tube.
とほぼ同大の粒状物である請求項１記載の多管式反応
器。3. The multitubular reactor according to claim 1, wherein the auxiliary filling material is a granular material having substantially the same size as the catalyst filled in the reaction tube.
が粉化等により体積減少した場合に、反応管に落ち込ん
で体積減少分を補う請求項１〜請求項３いずれか１項記
載の多管式反応器。4. The filling auxiliary substance falls into the reaction tube to compensate for the volume decrease when the volume of the catalyst filled in the reaction tube is reduced due to pulverization or the like. Multi-tube reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001379876A JP2003183003A (en) | 2001-12-13 | 2001-12-13 | Multi-tube reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001379876A JP2003183003A (en) | 2001-12-13 | 2001-12-13 | Multi-tube reactor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003183003A true JP2003183003A (en) | 2003-07-03 |
Family
ID=27591205
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006142299A (en) * | 2005-12-16 | 2006-06-08 | Sumitomo Chemical Co Ltd | Fixed-bed multitubular reactor |
| JP2007112667A (en) * | 2005-10-20 | 2007-05-10 | Tokyo Gas Co Ltd | Steam reformer |
| US7322405B2 (en) | 2004-12-22 | 2008-01-29 | Honda Motor Co., Ltd. | Multi-pipe heat exchanger apparatus and method of producing the same |
| KR101050263B1 (en) * | 2009-08-20 | 2011-07-19 | 주식회사 효성 | Proxy Reactor for Fuel Cell |
| US10118148B2 (en) | 2015-06-08 | 2018-11-06 | Ihi Corporation | Reactor |
-
2001
- 2001-12-13 JP JP2001379876A patent/JP2003183003A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7322405B2 (en) | 2004-12-22 | 2008-01-29 | Honda Motor Co., Ltd. | Multi-pipe heat exchanger apparatus and method of producing the same |
| JP2007112667A (en) * | 2005-10-20 | 2007-05-10 | Tokyo Gas Co Ltd | Steam reformer |
| JP2006142299A (en) * | 2005-12-16 | 2006-06-08 | Sumitomo Chemical Co Ltd | Fixed-bed multitubular reactor |
| KR101050263B1 (en) * | 2009-08-20 | 2011-07-19 | 주식회사 효성 | Proxy Reactor for Fuel Cell |
| US10118148B2 (en) | 2015-06-08 | 2018-11-06 | Ihi Corporation | Reactor |
| KR20200011620A (en) | 2015-06-08 | 2020-02-03 | 가부시키가이샤 아이에이치아이 | Reactor |
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