JP2003095610A - Method for producing hydrogen - Google Patents
Method for producing hydrogenInfo
- Publication number
- JP2003095610A JP2003095610A JP2001287571A JP2001287571A JP2003095610A JP 2003095610 A JP2003095610 A JP 2003095610A JP 2001287571 A JP2001287571 A JP 2001287571A JP 2001287571 A JP2001287571 A JP 2001287571A JP 2003095610 A JP2003095610 A JP 2003095610A
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- Japan
- Prior art keywords
- reaction
- catalyst layer
- wall
- oxygen
- hydrogen
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、都市ガス等の炭化
水素から水素又は水素を含む合成ガスを製造する水素製
造方法に関し、自動車あるいは家庭用発電等に有効な水
素製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen production method for producing hydrogen or a synthesis gas containing hydrogen from hydrocarbons such as city gas, and more particularly to a hydrogen production method effective for power generation for automobiles or households.
【０００２】[0002]
【従来の技術】周知の如く、化石燃料の内でもメタンは
水素含有量を最も多く含む。従来、このメタンから水素
を製造する場合、図５に示すように行なっている。図中
の符番１は、外壁２と内壁３からなる二重管構造の反応
管を示す。前記外壁２と内壁３で囲まれた領域の一部
（反応部）には、触媒がある一定の高さにわたって充填
されて触媒層４を形成している。また、前記反応管１内
の中央部には、起動時に触媒層４を外部加熱するための
バーナ５が配置されている。前記触媒層４にはＣＨ ４、
Ｈ２Ｏが送られ、触媒層４で下記式（１）のような水蒸
気改質反応（吸熱反応）が行なわれる。2. Description of the Related Art As is well known, methane is one of fossil fuels.
Contains the highest hydrogen content. Conventionally, hydrogen from this methane
Is manufactured as shown in FIG. In the figure
No. 1 is the reaction of double tube structure consisting of outer wall 2 and inner wall 3.
Shows a tube. Part of the area surrounded by the outer wall 2 and the inner wall 3
(Reaction part) is filled with catalyst over a certain height
Thus, the catalyst layer 4 is formed. In addition, in the reaction tube 1
In the central part of the
A burner 5 is arranged. CH in the catalyst layer 4 Four,
HTwoO is sent to the catalyst layer 4 and steamed as shown in the following formula (1).
A gas reforming reaction (endothermic reaction) is performed.
【０００３】 ＣＨ４＋Ｈ２Ｏ→ＣＯ＋３Ｈ２ …（１）CH 4 + H 2 O → CO + 3H 2 (1)
【０００４】[0004]
【発明が解決しようとする課題】このように、従来は起
動時にバーナを用いて外部加熱するため、伝熱効率が低
く、反応部の昇温に多くの時間がかかる。また、起動時
の温度分布が顕著になり、反応が定常状態になるまでに
も時間がかかるなどの問題点があった。図６は、従来技
術における反応管の長手方向に沿う距離と反応部及びそ
の周囲における温度との関係を示す特性図を示す。図６
に示すように、触媒層４の下部付近では温度が高いが、
それより上部側では触媒層４での吸熱反応により温度が
徐々に下がることが分かる。As described above, since the external heating is conventionally performed by using the burner at the time of starting, the heat transfer efficiency is low and it takes a long time to raise the temperature of the reaction part. Further, there is a problem that the temperature distribution at the time of start-up becomes remarkable and it takes time until the reaction reaches a steady state. FIG. 6 is a characteristic diagram showing the relationship between the distance along the longitudinal direction of the reaction tube and the temperature in the reaction part and its surroundings in the prior art. Figure 6
As shown in, the temperature is high near the bottom of the catalyst layer 4,
It can be seen that the temperature gradually decreases on the upper side due to the endothermic reaction in the catalyst layer 4.
【０００５】また、加熱用バーナの炊き込み量を多くす
れば反応部の昇温スピードを速めることができるが、触
媒層の温度分布が顕著になり、触媒の耐熱温度以上の高
温となるスポットが発生する可能性があるため、触媒の
耐久性の点から急激な昇温をすることができない。Further, if the amount of cooking of the heating burner is increased, the rate of temperature rise in the reaction section can be increased, but the temperature distribution of the catalyst layer becomes remarkable, and spots are generated that are higher than the heat resistant temperature of the catalyst. Therefore, the temperature cannot be rapidly increased from the viewpoint of durability of the catalyst.
【０００６】本発明は上記の課題を解決するためになさ
れたもので、外壁及び内壁からなる二重管構造の反応管
の反応部に触媒層を配置するとともに、反応管内にバー
ナを配置し、少なくとも起動時、炭化水素と水蒸気から
成る原料ガス中に空気又は酸素を注入して反応部内で酸
化反応を起こさせることにより、反応部の昇温を速やか
に行なって起動時間を短縮するとともに、加熱負荷を低
減しえる水素製造方法を提供することを目的とする。The present invention has been made to solve the above problems. A catalyst layer is arranged in the reaction part of a reaction tube having a double tube structure consisting of an outer wall and an inner wall, and a burner is arranged in the reaction tube. At least at startup, by injecting air or oxygen into the raw material gas consisting of hydrocarbons and steam to cause an oxidation reaction in the reaction part, the temperature of the reaction part is rapidly raised to shorten the start-up time and heat. An object of the present invention is to provide a hydrogen production method capable of reducing the load.
【０００７】また、本発明は、外壁及び内壁からなる二
重管構造の反応管の反応部に触媒層を配置し、少なくと
も起動時、炭化水素と水蒸気から成る原料ガス中に空気
又は酸素を注入して反応部内で酸化反応を起こさせるこ
とにより、上記と同様、反応部の昇温を速やかに行なっ
て起動時間を短縮するとともに、加熱負荷を低減しえる
水素製造方法を提供することを目的とする。さらに、二
重管の内管部にバーナの代わりに燃焼触媒を配置するこ
とにより、繊細な温度制御をすることを目的とする。Further, according to the present invention, a catalyst layer is arranged in the reaction part of a reaction tube having a double tube structure consisting of an outer wall and an inner wall, and air or oxygen is injected into a raw material gas consisting of hydrocarbon and steam at least at the time of starting. Then, by causing an oxidation reaction in the reaction part, similarly to the above, while increasing the temperature of the reaction part quickly to shorten the start-up time, it is an object to provide a hydrogen production method that can reduce the heating load. To do. Further, it is an object of the present invention to perform delicate temperature control by disposing a combustion catalyst instead of the burner in the inner pipe portion of the double pipe.
【０００８】[0008]
【課題を解決するための手段】本願第１の発明は、炭化
水素を水蒸気改質して水素又は水素を含む合成ガスを製
造する水素製造方法において、外壁及び内壁からなる二
重管構造の反応管の反応部に触媒層を配置するととも
に、反応管内にバーナを配置し、少なくとも起動時、炭
化水素と水蒸気から成る原料ガス中に空気又は酸素を注
入して反応部内で酸化反応を起こさせることを特徴とす
る水素製造方法である。The first invention of the present application is a hydrogen production method for producing hydrogen or a synthesis gas containing hydrogen by steam reforming a hydrocarbon, and a reaction of a double tube structure having an outer wall and an inner wall. A catalyst layer is placed in the reaction section of the tube, and a burner is placed in the reaction tube. At least at startup, air or oxygen is injected into the raw material gas consisting of hydrocarbons and steam to cause an oxidation reaction in the reaction section. Is a method for producing hydrogen.
【０００９】本願第２の発明は、炭化水素を水蒸気改質
して水素又は水素を含む合成ガスを製造する水素製造方
法において、外壁及び内壁からなる二重管構造の反応管
の反応部に触媒層を配置し、少なくとも起動時、炭化水
素と水蒸気から成る原料ガス中に空気又は酸素を注入し
て反応部内で酸化反応を起こさせることを特徴とする水
素製造方法である。A second invention of the present application is a method for producing hydrogen for steam reforming a hydrocarbon to produce hydrogen or a synthesis gas containing hydrogen, wherein a catalyst is provided in a reaction part of a reaction tube having a double-tube structure having an outer wall and an inner wall. A hydrogen producing method is characterized in that a layer is arranged, and at least at start-up, air or oxygen is injected into a raw material gas composed of hydrocarbon and steam to cause an oxidation reaction in a reaction section.
【００１０】[0010]
【発明の実施の形態】以下、本発明の水素製造方法につ
いて更に詳しく説明する。BEST MODE FOR CARRYING OUT THE INVENTION The hydrogen production method of the present invention will be described in more detail below.
【００１１】本発明において、少なくとも起動時に、炭
化水素と水蒸気から成る原料ガス中に空気又は酸素を注
入するのは、起動時における反応が特にバラツキやすい
からであり、起動時のみならず、その後も空気又は酸素
を炭化水素と水蒸気から成る原料ガス中に注入すること
もできる。ここで、空気（又は酸素）と炭化水素とＨ ２
Ｏの配合割合は、炭化水素の炭素数１ｍｏｌに対し、空
気０．５〜５ｍｏｌ(酸素０．１〜１ｍｏｌ）のように
することが好ましい。この理由は，加熱源にバーナ又は
燃焼触媒を用いない場合には炭化水素の水蒸気改質に使
われる熱量と同等以上の熱量を補う必要があること、加
熱源にバーナ又は燃焼触媒を用いる場合においても、補
助的に入熱することにより触媒の昇温を速やかにするこ
とができるためである。In the present invention, charcoal is used at least at startup.
Inject air or oxygen into the source gas consisting of hydrogen chloride and water vapor
It is especially easy to put the reaction in when starting up.
The air or oxygen not only at startup but also afterwards.
Injecting into a source gas consisting of hydrocarbons and steam
You can also Where air (or oxygen), hydrocarbons and H Two
The compounding ratio of O is empty for 1 mol of carbon number of hydrocarbon.
As in the case of 0.5 to 5 mol (0.1 to 1 mol of oxygen)
Preferably. The reason for this is that the heating source is a burner or
Used for steam reforming of hydrocarbons when no combustion catalyst is used.
It is necessary to supplement the amount of heat equal to or greater than the amount of heat
Even when a burner or combustion catalyst is used as the heat source,
The temperature of the catalyst can be raised quickly by supplementary heat input.
This is because you can
【００１２】本発明において、前記空気又は酸素は、前
記触媒層の積層方向に対して多段で供給することが好ま
しい。ここで、触媒層の段数は２つ以上であればよい。
これにより、空気等が触媒層に対してより均等に供給さ
れ、反応部内での酸化反応がより促進される。In the present invention, the air or oxygen is preferably supplied in multiple stages in the stacking direction of the catalyst layers. Here, the number of stages of the catalyst layer may be two or more.
As a result, air or the like is more evenly supplied to the catalyst layer, and the oxidation reaction in the reaction section is further promoted.
【００１３】本発明において、前記空気又は酸素を、前
記触媒層の円周方向に対して等間隔の位置から供給する
ことが好ましい。この場合も、上記と同じように、空気
等が触媒層に対してより均等に供給され、反応部内での
酸化反応がより促進される。In the present invention, it is preferable to supply the air or oxygen from positions at equal intervals in the circumferential direction of the catalyst layer. Also in this case, as in the above case, air or the like is supplied to the catalyst layer more evenly, and the oxidation reaction in the reaction section is further promoted.
【００１４】本発明において、前記反応管（内壁）の内
側に燃焼触媒層を配置し、この燃焼触媒層に夫々空気又
は酸素を注入することが好ましい。但し、この場合、内
壁に該内壁の周方向に沿って空気等を供給するための空
気供給穴を均等に設けることが好ましい。これにより、
従来のようにバーナを用いずに、反応部での昇温を速や
かに行なうとともに、触媒層の温度分布がフラットにな
り反応を効率的に起こすことができる。In the present invention, it is preferable to arrange a combustion catalyst layer inside the reaction tube (inner wall) and inject air or oxygen into the combustion catalyst layer. However, in this case, it is preferable that the inner wall be uniformly provided with air supply holes for supplying air or the like along the circumferential direction of the inner wall. This allows
It is possible to quickly raise the temperature in the reaction section without using a burner as in the conventional case, and to flatten the temperature distribution of the catalyst layer to efficiently cause the reaction.
【００１５】本発明において、前記触媒層、燃焼触媒層
を形成する触媒としては、ニッケル、コバルト、鉄、モ
リブデンから成る少なくとも一種類以上の遷移金属又は
その酸化物、或いはルテニウム、白金、ロジウム、パラ
ジウムから成る少なくとも一種類以上の貴金属又はその
酸化物を触媒成分とし、アルミナ、ジルコニア、ランタ
ニアのうち少なくとも一種類以上から成る酸化物或いは
複合酸化物を担体とする触媒等が挙げられる。In the present invention, as the catalyst for forming the catalyst layer and the combustion catalyst layer, at least one or more kinds of transition metals consisting of nickel, cobalt, iron and molybdenum or oxides thereof, or ruthenium, platinum, rhodium and palladium are used. A catalyst having at least one or more noble metal or oxide thereof as a catalyst component and an oxide or complex oxide as a carrier, which is at least one or more of alumina, zirconia, and lanthanum, is used.
【００１６】[0016]
【実施例】以下、本発明の各実施例について説明する。
なお、下記実施例で述べる各部材の材料や数値等の一例
を示すもので、本発明の権利範囲はこれにより限定され
るものではない。Embodiments of the present invention will be described below.
It should be noted that the examples of the materials, numerical values, etc. of the respective members described in the following examples are shown, and the scope of rights of the present invention is not limited thereby.
【００１７】（実施例１）図１を参照する。図中の符番
１１は、外壁１２と内壁１３からなる二重管構造のステ
ンレス製の反応管を示す。前記外壁１２と内壁１３で囲
まれた領域の一部には、例えば担体にアルミナを用いル
テニウムを触媒成分とする触媒がある一定の高さにわた
って充填されて触媒層１４を形成している。また、前記
反応管１１内の中央部には、起動時に触媒層１４を外部
加熱するためのバーナ１５が配置されている。前記触媒
層１４には、少なくとも起動時にＣＨ４、Ｈ２Ｏ等の原
料ガスの他、酸素（Ｏ２）が供給されるようになってい
る。Example 1 Reference is made to FIG. Reference numeral 11 in the figure denotes a stainless steel reaction tube having a double-tube structure including an outer wall 12 and an inner wall 13. A part of the region surrounded by the outer wall 12 and the inner wall 13 is filled with a catalyst having a catalyst component of ruthenium using alumina as a carrier over a certain height to form a catalyst layer 14. In addition, a burner 15 for externally heating the catalyst layer 14 at the time of startup is arranged in the center of the reaction tube 11. Oxygen (O 2 ) is supplied to the catalyst layer 14 at least at the time of startup, in addition to source gases such as CH 4 and H 2 O.
【００１８】なお、改質部に供給する原料ガスは触媒１
体積当たりＣＨ４１０００体積に対しＨ２Ｏ２０００、
Ａｉｒ１０００の体積比で供給し、バーナ部に供給する
ガスはＣＨ４２４０、Ａｉｒ２４００とした。この流量
比はメタンが水蒸気改質するのに要する熱量の１．５倍
比の入熱量で反応が維持できることを意味する。また触
媒を充填している反応部の内管壁１３とバーナ１５の火
炎部は触媒部が１０００℃を越えないように約３０ｍｍ
の距離とした。The raw material gas supplied to the reforming section is the catalyst 1
H 2 O 2000 for 1000 volumes of CH 4 per volume,
The gas supplied at a volume ratio of Air 1000 and the gas supplied to the burner part was CH 4 240 and Air 2400. This flow rate ratio means that the reaction can be maintained with a heat input amount of 1.5 times the heat amount required for steam reforming of methane. Also, the inner tube wall 13 of the reaction section filled with the catalyst and the flame section of the burner 15 are about 30 mm so that the temperature of the catalyst section does not exceed 1000 ° C.
And the distance.
【００１９】このように、実施例１では、起動時に触媒
層１４にＣＨ４，Ｈ２Ｏ，Ｏ２を適宜な配合割合で供給
して反応部内で直接酸化反応を起こさせるため、昇温を
速やかに行なうとともに、図２に示されるように触媒層
１４の温度分布がフラットになり反応を効率的に起こす
ことができる。なお、図２において、「予熱部」（バー
ナ部）とは、加熱バーナ１５の炎の最下部から触媒層１
４の入口直前までを示す。さらに、反応の熱源にバーナ
のみを用いる従来法では、メタンの水蒸気改質で必要と
する熱量の約３倍の入熱量が必要となるのに対し、本発
明では１．５倍量と少なくでき、加熱バーナ１５の小型
化、１３の伝熱面積の減少化を図ることができるため装
置のコンパクト化が可能となる。従って、実施例１によ
る方法を例えば自動車用の燃料電池の駆動に利用する場
合、起動時間を短縮し、装置のコンパクト化を図ること
ができる。As described above, in Example 1, since CH 4 , H 2 O and O 2 are supplied to the catalyst layer 14 at an appropriate mixing ratio at the time of start-up to cause an oxidation reaction directly in the reaction section, the temperature is raised. The reaction can be carried out promptly, and the temperature distribution of the catalyst layer 14 becomes flat as shown in FIG. 2 to allow the reaction to occur efficiently. In addition, in FIG. 2, the “preheating part” (burner part) means the catalyst layer 1 from the bottom of the flame of the heating burner 15.
It shows just before the entrance of No. 4. Further, in the conventional method using only the burner as the heat source for the reaction, the heat input amount that is about 3 times the heat amount required for steam reforming of methane is required, whereas in the present invention it can be reduced to 1.5 times the amount. Since the heating burner 15 can be downsized and the heat transfer area of 13 can be reduced, the apparatus can be downsized. Therefore, when the method according to the first embodiment is used for driving a fuel cell for an automobile, for example, it is possible to shorten the start-up time and make the apparatus compact.
【００２０】（比較例）図５に示される装置を用い、反
応管中にＯ２（空気）を供給しないこと以外は実施例１
と全て同一の実施方法とした。なお、改質部に供給する
原料ガスは触媒１体積当たりＣＨ４９００体積に対しＨ
２Ｏ２０００で供給し、バーナ部に供給するガスはＣＨ
４６８０、Ａｉｒ６８００とした。この流量比はメタン
が水蒸気改質するのに要する熱量の３倍比の入熱量で反
応が維持できることを意味する。(Comparative Example) Example 1 was carried out using the apparatus shown in FIG. 5 except that O 2 (air) was not supplied into the reaction tube.
The same implementation method was used. The raw material gas supplied to the reforming unit was H 4 per volume of CH 4 900 per volume of catalyst.
2 O2000 is supplied, and the gas supplied to the burner is CH
4 680 and Air 6800. This flow rate ratio means that the reaction can be maintained with a heat input amount that is three times the heat amount required for steam reforming of methane.
【００２１】このように比較例１では、改質反応部と加
熱部がそれぞれ分割しているため、昇温が速やかでない
ばかりか、図６に示されるように実施例１と比較して触
媒層１４の温度分布が大きくなる。従って反応効率の低
下、バーナ及び伝熱面積の大容量化に伴う装置の大型化
が問題になる可能性がある。As described above, in Comparative Example 1, since the reforming reaction section and the heating section are separated from each other, the temperature rise is not rapid and, as shown in FIG. The temperature distribution of 14 becomes large. Therefore, there is a possibility that the reaction efficiency may be lowered and that the burner and the heat transfer area may be increased in capacity to make the apparatus larger.
【００２２】（実施例２）図３（Ａ），（Ｂ）を参照す
る。ここで、図３（Ａ）は実施例２に係る反応管の概略
断面図、図３（Ｂ）は図３（Ａ）の平面図を示す。但
し、図１と同部材は同符番を付して説明を省略する。本
実施例２はバーナレスタイプで、反応管１１の外壁１２
の多段（３段）でかつ周方向に沿って均等に酸素注入穴
１６を設け、触媒層１４にＣＨ４，Ｈ２Ｏを供給する一
方、前記触媒層１４に前記酸素注入穴１６からＯ２を供
給することを特徴とする。(Embodiment 2) Reference is made to FIGS. 3 (A) and 3 (B). Here, FIG. 3A is a schematic cross-sectional view of the reaction tube according to Example 2, and FIG. 3B is a plan view of FIG. 3A. However, the same members as those in FIG. The second embodiment is a burnerless type and has an outer wall 12 of the reaction tube 11.
Oxygen injection holes 16 are evenly provided along the circumferential direction in multiple stages (3 steps), and while CH 4 and H 2 O are supplied to the catalyst layer 14, the catalyst layer 14 is supplied with O 2 from the oxygen injection holes 16 It is characterized by supplying.
【００２３】実施例２によれば、実施例１と同様に、昇
温を速やかに行なうとともに、図４に示されるように触
媒層１４の温度分布がフラットになり反応を効率的に起
こすことができる。さらに、反応の熱源にバーナのみを
用いる従来法では、メタンの水蒸気改質で必要とする熱
量の約３倍の入熱量が必要となるのに対し、本発明では
１．５倍量と少なくでき、加熱バーナ１５の小型化、１
３の伝熱面積の減少化を図ることができるため装置のコ
ンパクト化が可能となる。従って、実施例２による方法
を例えば自動車用の燃料電池の駆動に利用する場合、起
動時間を短縮し、装置のコンパクト化を図ることができ
る。According to the second embodiment, similarly to the first embodiment, the temperature is rapidly raised, and the temperature distribution of the catalyst layer 14 becomes flat as shown in FIG. 4, so that the reaction can occur efficiently. it can. Further, in the conventional method using only the burner as the heat source for the reaction, the heat input amount that is about 3 times the heat amount required for steam reforming of methane is required, whereas in the present invention it can be reduced to 1.5 times the amount. , Miniaturization of heating burner 15, 1
Since the heat transfer area of 3 can be reduced, the device can be made compact. Therefore, when the method according to the second embodiment is used for driving a fuel cell for an automobile, for example, the start-up time can be shortened and the device can be made compact.
【００２４】（実施例３）図７を参照する。但し、図１
と同部材は同符番を付して説明を省略する。本実施例３
は、反応管１１の内壁１２の内側に多段（例えば４段）
に燃焼触媒層１７を設けるとともに、この燃焼触媒層１
７が位置する内壁１２に該内壁１２の周方向に沿って均
等に酸素注入穴（図示せず）を例えば４個穿設し、反応
管１１の内壁１２、外壁１３間の触媒層１４にＯ２をＣ
Ｈ４，Ｈ２Ｏとともに供給するとともに、酸素注入穴よ
り燃焼触媒層１７にも供給することを特徴とする。(Embodiment 3) Referring to FIG. However, in FIG.
The same members as and are denoted by the same reference numerals, and description thereof will be omitted. Example 3
Is a multi-stage (for example, 4 stages) inside the inner wall 12 of the reaction tube 11.
The combustion catalyst layer 17 is provided on the
For example, four oxygen injection holes (not shown) are evenly formed in the inner wall 12 where the inner wall 7 is located along the circumferential direction of the inner wall 12, and the catalyst layer 14 between the inner wall 12 and the outer wall 13 of the reaction tube 11 is filled with O. 2 for C
It is characterized in that it is supplied together with H 4 and H 2 O and also supplied to the combustion catalyst layer 17 through the oxygen injection hole.
【００２５】実施例３によれば、反応管１１の内壁の内
側に燃焼触媒層１７を配置し、内壁１２・外壁１３間の
触媒層１４のみならず、燃焼触媒層１７にもＯ２を供給
するようになっているため、従来のようにバーナを用い
ずに、昇温を速やかに行なうとともに、触媒層１４の温
度分布がフラットになり反応を効率的に起こすことがで
きる。従って、実施例３による方法を例えば自動車用の
燃料電池の駆動に利用する場合、起動時間を短縮し、装
置のコンパクト化を図ることができる。According to the third embodiment, the combustion catalyst layer 17 is arranged inside the inner wall of the reaction tube 11, and O 2 is supplied not only to the catalyst layer 14 between the inner wall 12 and the outer wall 13 but also to the combustion catalyst layer 17. Therefore, it is possible to raise the temperature quickly without using a burner as in the conventional case, and to flatten the temperature distribution of the catalyst layer 14 to efficiently cause the reaction. Therefore, when the method according to the third embodiment is used for driving a fuel cell for an automobile, for example, the start-up time can be shortened and the device can be made compact.
【００２６】[0026]
【発明の効果】以上詳記したように本発明によれば、外
壁及び内壁からなる二重管構造の反応管の反応部に触媒
層を配置するとともに、反応管内にバーナを配置し、少
なくとも起動時、炭化水素と水蒸気から成る原料ガス中
に空気又は酸素を注入して反応部内で酸化反応を起こさ
せることにより、反応部の昇温を速やかに行なって起動
時間を短縮するとともに、加熱負荷を低減しえる水素製
造方法を提供できる。As described in detail above, according to the present invention, the catalyst layer is arranged in the reaction part of the reaction tube having the double-walled structure consisting of the outer wall and the inner wall, and the burner is arranged in the reaction tube to start at least At this time, by injecting air or oxygen into the raw material gas consisting of hydrocarbons and steam to cause an oxidation reaction in the reaction part, the temperature of the reaction part is rapidly raised to shorten the start-up time and heat load. It is possible to provide a method for producing hydrogen that can be reduced.
【００２７】また、本発明は、外壁及び内壁からなる二
重管構造の反応管の反応部に触媒層を配置し、少なくと
も起動時、炭化水素と水蒸気から成る原料ガス中に空気
又は酸素を注入して反応部内で酸化反応を起こさせるこ
とにより、上記と同様、反応部の昇温を速やかに行なっ
て起動時間を短縮するとともに、加熱負荷を低減しえる
水素製造方法を提供できる。Further, according to the present invention, a catalyst layer is arranged in the reaction part of a reaction tube having a double tube structure consisting of an outer wall and an inner wall, and air or oxygen is injected into a raw material gas composed of hydrocarbon and steam at least at the time of starting. Then, by causing an oxidation reaction in the reaction section, similarly to the above, it is possible to provide a hydrogen production method capable of rapidly raising the temperature of the reaction section to shorten the start-up time and reduce the heating load.
【図１】本発明の実施例１に係る水素製造方法の概略説
明図。FIG. 1 is a schematic explanatory diagram of a hydrogen production method according to a first embodiment of the present invention.
【図２】図１の水素製造方法による反応管の長手方向に
沿う距離と反応部及びその周囲における温度との関係を
示す特性図。2 is a characteristic diagram showing the relationship between the distance along the longitudinal direction of the reaction tube and the temperature in the reaction part and its surroundings according to the hydrogen production method of FIG.
【図３】本発明の実施例２に係る水素製造方法の概略説
明図。FIG. 3 is a schematic explanatory diagram of a hydrogen production method according to a second embodiment of the present invention.
【図４】図３の水素製造方法による反応管の長手方向に
沿う距離と反応部及びその周囲における温度との関係を
示す特性図。FIG. 4 is a characteristic diagram showing the relationship between the distance along the longitudinal direction of the reaction tube and the temperature in the reaction part and its surroundings according to the hydrogen production method of FIG.
【図５】従来の水素製造方法の概略説明図。FIG. 5 is a schematic explanatory view of a conventional hydrogen production method.
【図６】従来方法による反応管の長手方向に沿う距離と
反応部及びその周囲における温度との関係を示す特性
図。FIG. 6 is a characteristic diagram showing the relationship between the distance along the longitudinal direction of the reaction tube and the temperature in the reaction section and its surroundings according to the conventional method.
【図７】本発明の実施例３に係る水素製造方法の概略説
明図。FIG. 7 is a schematic explanatory diagram of a hydrogen production method according to a third embodiment of the present invention.
１１…反応管、 １２…外壁、 １３…内壁、 １４…触媒層、 １５…バーナ、 １６…酸素注入穴、 １７…燃焼触媒層。 11 ... Reaction tube, 12 ... outer wall, 13 ... inner wall, 14 ... Catalyst layer, 15 ... Burner, 16 ... Oxygen injection hole, 17 ... Combustion catalyst layer.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 渡邊 悟 広島県広島市西区観音新町四丁目６番22号 三菱重工業株式会社広島研究所内 (72)発明者 米村 将直 広島県広島市西区観音新町四丁目６番22号 三菱重工業株式会社広島研究所内 (72)発明者 吉田 博久 広島県広島市西区観音新町四丁目６番22号 三菱重工業株式会社広島研究所内 Ｆターム(参考） 4G040 EA03 EA06 EB14 EB24 EB27 EB43 EB46 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Satoru Watanabe 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture Mitsubishi Heavy Industries Ltd. Hiroshima Research Center (72) Inventor Masanao Yonemura 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture Mitsubishi Heavy Industries Ltd. Hiroshima Research Center (72) Inventor Hirohisa Yoshida 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture Mitsubishi Heavy Industries Ltd. Hiroshima Research Center F-term (reference) 4G040 EA03 EA06 EB14 EB24 EB27 EB43 EB46
Claims (5)
を含む合成ガスを製造する水素製造方法において、外壁
及び内壁からなる二重管構造の反応管の反応部に触媒層
を配置するとともに、反応管の内管にバーナを配置し、
少なくとも起動時、炭化水素と水蒸気から成る原料ガス
中に空気又は酸素を注入して反応部内で酸化反応を起こ
させることを特徴とする水素製造方法。1. A hydrogen production method for producing hydrogen or a synthesis gas containing hydrogen by steam reforming a hydrocarbon, wherein a catalyst layer is arranged in a reaction part of a reaction tube having a double tube structure having an outer wall and an inner wall. , Place a burner in the inner tube of the reaction tube,
A hydrogen production method characterized by injecting air or oxygen into a raw material gas consisting of hydrocarbons and steam at least at startup to cause an oxidation reaction in a reaction section.
を含む合成ガスを製造する水素製造方法において、外壁
及び内壁からなる二重管構造の反応管の反応部に触媒層
を配置し、少なくとも起動時、炭化水素と水蒸気から成
る原料ガス中に空気又は酸素を注入して反応部内で酸化
反応を起こさせることを特徴とする水素製造方法。2. In a hydrogen production method for producing hydrogen or a synthesis gas containing hydrogen by steam reforming a hydrocarbon, a catalyst layer is disposed in a reaction part of a reaction tube having a double-tube structure having an outer wall and an inner wall, A hydrogen production method characterized by injecting air or oxygen into a raw material gas consisting of hydrocarbons and steam at least at startup to cause an oxidation reaction in a reaction section.
方向に対して多段で供給することを特徴とする請求項２
記載の水素製造方法。3. The air or oxygen is supplied in multiple stages in the stacking direction of the catalyst layers.
The hydrogen production method described.
方向に対して等間隔の位置から供給することを特徴とす
る請求項２記載の水素製造方法。4. The method for producing hydrogen according to claim 2, wherein the air or oxygen is supplied from positions at equal intervals in the circumferential direction of the catalyst layer.
し、この燃焼触媒層に炭化水素及び空気又は酸素を注入
することを特徴とする請求項２記載の水素製造方法。5. The method for producing hydrogen according to claim 2, wherein a combustion catalyst layer is arranged on the inner tube side of the reaction tube, and hydrocarbon and air or oxygen is injected into the combustion catalyst layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001287571A JP2003095610A (en) | 2001-09-20 | 2001-09-20 | Method for producing hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001287571A JP2003095610A (en) | 2001-09-20 | 2001-09-20 | Method for producing hydrogen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003095610A true JP2003095610A (en) | 2003-04-03 |
Family
ID=19110357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001287571A Withdrawn JP2003095610A (en) | 2001-09-20 | 2001-09-20 | Method for producing hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003095610A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100684771B1 (en) | 2005-09-27 | 2007-02-20 | 삼성에스디아이 주식회사 | Apparatus for reforming fuel and driving method of the same |
| US7682587B2 (en) | 2005-07-29 | 2010-03-23 | Samsung Sdi Co., Ltd. | Fuel cell reformer |
| US8017088B2 (en) | 2005-09-27 | 2011-09-13 | Samsung Sdi Co., Ltd. | Fuel reformer |
-
2001
- 2001-09-20 JP JP2001287571A patent/JP2003095610A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7682587B2 (en) | 2005-07-29 | 2010-03-23 | Samsung Sdi Co., Ltd. | Fuel cell reformer |
| KR100684771B1 (en) | 2005-09-27 | 2007-02-20 | 삼성에스디아이 주식회사 | Apparatus for reforming fuel and driving method of the same |
| US8017088B2 (en) | 2005-09-27 | 2011-09-13 | Samsung Sdi Co., Ltd. | Fuel reformer |
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