JP2002104808A - Method of reforming fuel - Google Patents
Method of reforming fuelInfo
- Publication number
- JP2002104808A JP2002104808A JP2000299102A JP2000299102A JP2002104808A JP 2002104808 A JP2002104808 A JP 2002104808A JP 2000299102 A JP2000299102 A JP 2000299102A JP 2000299102 A JP2000299102 A JP 2000299102A JP 2002104808 A JP2002104808 A JP 2002104808A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- hydrocarbon
- steam
- fuel
- 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
- 239000000446 fuel Substances 0.000 title claims abstract description 53
- 238000002407 reforming Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000000629 steam reforming Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 239000010970 precious metal Substances 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910000510 noble metal Inorganic materials 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 150000002739 metals Chemical class 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 40
- 210000004027 cell Anatomy 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000005518 polymer electrolyte Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- -1 CH 4 Chemical class 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸素あるいは空気
と炭化水素，水蒸気を用いて水素を主成分とするガスを
生成する燃料改質方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel reforming method for producing a gas containing hydrogen as a main component by using oxygen or air, a hydrocarbon, and steam.
【０００２】[0002]
【従来の技術】燃料改質器は、炭化水素と水蒸気を原料
とし、水素を主成分とするガスを生成する装置であり、
燃料電池の燃料である水素の供給装置として知られてい
る。2. Description of the Related Art A fuel reformer is a device that generates a gas containing hydrogen and steam as raw materials and containing hydrogen as a main component.
It is known as a supply device of hydrogen which is a fuel of a fuel cell.
【０００３】近年、燃料電池システムは、自動車用や家
庭用の電源システムとしての用途が期待されている。そ
のため、燃料電池本体のみならず、燃料電池の燃料とな
る水素を生成する燃料改質器においても、小型化や起動
時間の短縮が求められている。In recent years, fuel cell systems are expected to be used as power systems for automobiles and homes. Therefore, not only the fuel cell body but also a fuel reformer that generates hydrogen serving as a fuel of the fuel cell is required to be reduced in size and start-up time.
【０００４】燃料改質器の内部で進行する水蒸気改質反
応について、メタンを原料とした場合を例に説明する。[0004] The steam reforming reaction which proceeds inside the fuel reformer will be described by taking as an example the case where methane is used as a raw material.
【０００５】水蒸気改質反応は、式（１）に示すよう
に、メタンと水蒸気を反応させて水素を生成する反応
で、通常、その反応温度は７５０〜８５０℃で、反応速
度を上げるためにニッケル系等の触媒が使用される。[0005] The steam reforming reaction is a reaction for producing hydrogen by reacting methane and steam, as shown in the equation (1). Usually, the reaction temperature is 750 to 850 ° C. A nickel-based catalyst or the like is used.
【０００６】[0006]
【化１】 ＣＨ4＋Ｈ2Ｏ ⇔ ＣＯ＋３Ｈ2 …（１） 上記式（１）の反応は吸熱反応であり、この反応を促
進、継続させるためには熱源が必要である。従来のチュ
ーブラ型やプレート型の燃料改質器では、触媒を充填し
た改質部を、外部から加熱する間接加熱式であるため
に、燃料電池の負荷増減時や起動・停止時の追従性が著
しく悪いと云う問題があった。Embedded image CH 4 + H 2 O⇔CO + 3H 2 (1) The reaction of the above formula (1) is an endothermic reaction, and a heat source is required to promote and continue this reaction. Conventional tubular and plate-type fuel reformers use an indirect heating method, in which the reforming section filled with catalyst is heated from the outside. There was a problem that it was extremely bad.
【０００７】これに対し、外部加熱に加えて、燃料改質
器に空気または酸素を供給し、改質触媒上で、部分酸化
反応を併発させることにより反応熱を発生させ、燃料改
質器の内部からも加熱して、負荷追従性を向上するよう
にした燃料改質器が知られている（例えば、特開平１−
１８６５７０号、特開平２−１６０６０３号公報）。On the other hand, in addition to external heating, air or oxygen is supplied to the fuel reformer, and a partial oxidation reaction is caused on the reforming catalyst to generate heat of reaction. 2. Description of the Related Art A fuel reformer that heats from the inside to improve load following performance is known (for example, Japanese Patent Application Laid-Open No.
186570, JP-A-2-160603).
【０００８】[0008]
【発明が解決しようとする課題】前記の燃料改質器で
は、起動停止時や負荷変動時において、炭化水素の供給
量と、部分酸化用に供給する酸素量または空気量を独立
して制御することにより改質器の内部温度を調節してお
り、その制御は非常に複雑であった。In the above-mentioned fuel reformer, the amount of supply of hydrocarbons and the amount of oxygen or air supplied for partial oxidation are independently controlled at the time of starting and stopping or at the time of load fluctuation. Thus, the internal temperature of the reformer was adjusted, and the control was very complicated.
【０００９】また、水蒸気改質反応速度よりも酸化反応
速度が速いために、酸素濃度の高いガスの入口側では、
主に部分酸化反応が進行して温度が高くなり、改質器内
部に温度分布が生じると云う問題があった。Further, since the oxidation reaction rate is higher than the steam reforming reaction rate, the inlet side of the gas having a high oxygen concentration has
There has been a problem that the temperature is increased mainly due to the progress of the partial oxidation reaction, and a temperature distribution is generated inside the reformer.
【００１０】本発明の目的は、上記に鑑み、酸化反応の
発熱量と水蒸気改質反応の吸熱量をバランスさせた燃料
改質方法を提供することにある。[0010] In view of the above, an object of the present invention is to provide a fuel reforming method in which the calorific value of the oxidation reaction and the heat absorption amount of the steam reforming reaction are balanced.
【００１１】[0011]
【課題を解決するための手段】上記課題を解決する本発
明の要旨は次のとおりである。The gist of the present invention for solving the above problems is as follows.
【００１２】酸素または空気と炭化水素，水蒸気を含む
原料ガスを、前記炭化水素の酸化反応および前記炭化水
素の水蒸気改質反応を同時に促進する活性成分を有する
触媒と接触させることにより、外部から熱を与えずに水
素を製造することを特徴とする燃料改質方法にある。By contacting a raw material gas containing oxygen or air with hydrocarbons and steam with a catalyst having an active component which simultaneously promotes the oxidation reaction of the hydrocarbons and the steam reforming reaction of the hydrocarbons, heat from the outside is obtained. Fuel reforming method characterized by producing hydrogen without applying hydrogen.
【００１３】即ち、前記炭化水素の酸化反応を促進する
活性成分と、前記炭化水素の水蒸気改質活性を促進する
活性成分の担持量を調整して、酸化反応の発熱量と水蒸
気改質反応の吸熱量をバランスさせ、触媒全体を所望の
温度に維持する燃料改質方法にある。That is, by adjusting the amount of the active component that promotes the oxidation reaction of the hydrocarbon and the amount of the active component that promotes the steam reforming activity of the hydrocarbon, the calorific value of the oxidation reaction and the amount of the steam reforming reaction are adjusted. There is a fuel reforming method that balances the amount of heat absorbed and maintains the entire catalyst at a desired temperature.
【００１４】前記触媒として、少なくともＡｌを含む酸
化物で構成された多孔質担体に、Ｐｄ，Ｐｔ，Ｒｕ，Ｒ
ｈの貴金属および／または前記貴金属とＮｉ，Ｃｏ，Ｆ
ｅ，Ａｇ，Ｃｕ，Ｚｎ，Ｃｒ，希土類の少なくとも１種
を担持した触媒を用いる。[0014] As the catalyst, Pd, Pt, Ru, R
h and / or the noble metal and Ni, Co, F
A catalyst supporting at least one of e, Ag, Cu, Zn, Cr and rare earth is used.
【００１５】酸素または空気と炭化水素，水蒸気を本発
明の触媒と接触させることにより、以下の反応が起こ
る。The following reaction takes place by bringing oxygen or air into contact with a hydrocarbon or steam with the catalyst of the present invention.
【００１６】[0016]
【化２】 ＣＨ4＋Ｈ2Ｏ ⇔ ＣＯ＋３Ｈ2 …（１） ＣＨ4＋２Ｏ2 → ＣＯ2＋２Ｈ2Ｏ …（２） 式（２）の反応は大きな発熱反応であり、例えば、１％
のＣＨ4が式（２)で反応するとガスの温度は約３５０℃
に上昇する。これに対して式（１)では前述したように
大きな吸熱反応であるため、反応を継続するには常時外
部から熱を供給する必要がある。CH 4 + H 2 O⇔CO + 3H 2 (1) CH 4 + 2O 2 → CO 2 + 2H 2 O (2) The reaction of the formula (2) is a large exothermic reaction, for example, 1%
Of CH 4 reacts according to the formula (2), the gas temperature becomes about 350 ° C.
To rise. On the other hand, in the formula (1), since the reaction is a large endothermic reaction as described above, it is necessary to constantly supply heat from the outside to continue the reaction.
【００１７】本発明では、同一触媒上で式（１）、式
（２）を同時に起こすことにより、外部から熱を供給せ
ずに式（１）の反応を継続する点に特徴がある。The present invention is characterized in that the formula (1) and the formula (2) occur simultaneously on the same catalyst, so that the reaction of the formula (1) is continued without supplying heat from the outside.
【００１８】図１は、酸化反応を促進する活性点として
Ｐｄを、水蒸気改質反応を促進する活性点としてＮｉを
担持させた触媒の場合を例に、触媒上での反応を模式化
して示した模式図である。FIG. 1 schematically shows a reaction on a catalyst in which Pd is supported as an active point for promoting an oxidation reaction and Ni is supported as an active point for promoting a steam reforming reaction. FIG.
【００１９】Ｐｄ上においては主に式（２）の反応が起
って熱エネルギΔＥが発生し（）、発生したΔＥが近
傍のＮｉに伝達される（）。このΔＥを利用してＮｉ
上では主に式（１）の反応が起こり（）、水素を製造
することができる。On Pd, the reaction of equation (2) mainly occurs to generate heat energy ΔE (), and the generated ΔE is transmitted to nearby Ni (). Using this ΔE, Ni
Above, the reaction of the formula (1) occurs mainly (), and hydrogen can be produced.
【００２０】このように、本発明によれば、外部加熱、
即ち、反応管外壁を通しての伝熱によらず、発生した反
応熱により直接触媒層全体が加熱されるため、負荷追従
性を著しく向上することができる。Thus, according to the present invention, external heating,
In other words, the entire catalyst layer is directly heated by the generated reaction heat without relying on the heat transfer through the outer wall of the reaction tube, so that the load following ability can be significantly improved.
【００２１】また、触媒層のいずれの個所においても酸
化反応の発熱量と、水蒸気改質反応の吸熱量がバランス
しているため、触媒層内部の温度分布が改善される。Further, since the calorific value of the oxidation reaction and the endothermic amount of the steam reforming reaction are balanced in any part of the catalyst layer, the temperature distribution inside the catalyst layer is improved.
【００２２】また、起動時には、原料ガスの組成を変え
ずに装置が保有する熱容量の分だけ供給量を増やすこと
で容易に昇温ができる。さらに、負荷変動時において
も、原料ガスの組成を変えずに、供給量を変えるだけで
実質的に温度変化を伴わずに水素製造量の増減ができ
る。At the time of startup, the temperature can be easily raised by increasing the supply amount by the heat capacity of the apparatus without changing the composition of the source gas. Further, even at the time of load fluctuation, the hydrogen production amount can be increased or decreased substantially without a temperature change by merely changing the supply amount without changing the composition of the source gas.
【００２３】酸素または空気と炭化水素，水蒸気を原料
として水素を主成分とするガスを生成する燃料改質器に
おいても、前記原料中の炭化水素の酸化反応と水蒸気改
質反応とを一定の割合で促進する機能を有する触媒は重
要な役割を果たす。従って、本発明のキーポイントでも
ある。この触媒について以下に詳述する。In a fuel reformer which generates a gas containing hydrogen as a main component using oxygen or air, hydrocarbons and steam as raw materials, the oxidation reaction of hydrocarbons in the raw materials and the steam reforming reaction are performed at a constant rate. The catalyst having the function of promoting the reaction plays an important role. Therefore, it is also a key point of the present invention. This catalyst is described in detail below.
【００２４】まず、前記式（２）に示したような炭化水
素を酸化するための触媒としては、７００℃以上の耐熱
性と、できるだけ低温で着火するための低温活性が必要
となる。このためには、アルミナ，シリカ，シリカ−ア
ルミナ等を含む多孔質セラミックス担体に、活性成分と
してＰｄ，Ｐｔ，Ｒｕ，Ｒｈ等の貴金属やＡｇ，Ｍｎ，
Ｃｏ等の遷移金属を担持した触媒が良い。特に、Ｐｄ，
Ｍｎ，Ａｇが有効である。First, a catalyst for oxidizing hydrocarbons represented by the above formula (2) needs to have heat resistance of 700 ° C. or higher and low-temperature activity for igniting at as low a temperature as possible. For this purpose, noble metals such as Pd, Pt, Ru, Rh, Ag, Mn, and the like are added to a porous ceramics carrier containing alumina, silica, silica-alumina and the like.
A catalyst supporting a transition metal such as Co is preferable. In particular, Pd,
Mn and Ag are effective.
【００２５】これらの元素の近傍に、式（１）を促進す
るための活性成分である貴金属、Ｎｉ，Ｃｏ，Ｆｅ，Ａ
ｇ，Ｃｕ，Ｚｎ，Ｃｒ，希土類の少なくとも１種を担持
する。これにより同一触媒表面上で、同時に式（１）と
式（２）の反応が起こり、水素を製造することができ
る。In the vicinity of these elements, noble metals, Ni, Co, Fe, A, which are active components for promoting the formula (1),
g, Cu, Zn, Cr, and at least one of rare earths. As a result, the reactions of the formulas (1) and (2) occur simultaneously on the same catalyst surface, and hydrogen can be produced.
【００２６】これらの中では、特に、希土類・β−アル
ミナ、特に、Ｌａ・β−アルミナを担体とし、式（１）
の反応を活性化する成分としてＮｉ，Ｒｕ、式（２）の
反応を活性化する成分としてＰｄ，Ｐｔを担持した触媒
が有効である。なお、β−アルミナとはβ構造のアルミ
ナを意味する。また、Ｌａ・β−アルミナとしては、Ｌ
ａとアルミナのモル比が５：９５で、Ｌａを含むβ構造
のアルミナが好ましい。Among these, in particular, rare earth / β-alumina, particularly La · β-alumina, is used as a carrier, and the formula (1)
It is effective to use Ni, Ru as a component for activating the reaction of Pd and Pd, Pt as a component for activating the reaction of the formula (2). Here, β-alumina means alumina having a β structure. In addition, as La · β-alumina, L
The alumina having a β-structure containing La at a molar ratio of a to alumina of 5:95 is preferable.
【００２７】次に、触媒形状は、通常、製造の容易さか
ら粒状が多く用いられるが、圧力損失、熱容量が小さい
等の利点からモノリシス構造体が望ましい。Next, the catalyst is usually used in a granular form for ease of production. However, a monolithic structure is desirable because of its advantages such as low pressure loss and small heat capacity.
【００２８】モノリシス構造体の材質としては、通常の
コージェライト，ムライト，炭化ケイ素，アルミナ、並
びに、熱伝導率が高い金属も有効である。これらの構造
体の表面に前記の多孔質担体をコーティングし、さらに
前記のＰｄ，Ｐｔ，Ｒｕ，Ｒｈなどの貴金属および／ま
たは前記貴金属とＮｉ，Ｃｏ，Ｆｅ，Ａｇ，Ｃｕ，Ｚ
ｎ，Ｃｒ，希土類の少なくとも１種を担持させる。触媒
をモノリシス構造にすることにより、粒状の触媒におい
て問題があったガスの通気抵抗を低減することができ
る。As the material of the monolithic structure, ordinary cordierite, mullite, silicon carbide, alumina, and metals having high thermal conductivity are also effective. The surface of these structures is coated with the above-mentioned porous carrier, and the above-mentioned noble metals such as Pd, Pt, Ru, Rh and / or the above-mentioned noble metals and Ni, Co, Fe, Ag, Cu, Z
At least one of n, Cr and rare earth is supported. By making the catalyst have a monolithic structure, the gas flow resistance, which has a problem with the granular catalyst, can be reduced.
【００２９】また、粒状の担体に比べてモノリシス構造
の担体は、担体自体の熱容量が小さくなるため、触媒層
全体が所定の温度に達するまでの時間を短縮することが
できる。さらに、モノリシス構造の触媒担体を熱伝導率
の高い金属製にすることにより、起動停止時や負荷変動
時に、触媒全体の温度分布が解消するに要する時間を著
しく短縮することができる。Further, since the heat capacity of the carrier itself of the monolithic structure is smaller than that of the granular carrier, the time required for the entire catalyst layer to reach a predetermined temperature can be shortened. Furthermore, by making the catalyst carrier having a monolithic structure made of a metal having a high thermal conductivity, the time required for eliminating the temperature distribution of the entire catalyst at the time of starting and stopping or a load change can be significantly reduced.
【００３０】さらに触媒としては、式（１）と式（２）
の反応を同一触媒表面でなく、式（１）の反応を促進す
る触媒と、式（２）の反応を促進する触媒とを均一に混
合したものでもよい。但し、この場合、同一触媒上での
反応に比べて熱伝導効率が劣るため、若干、水素製造効
率が低下するが、有効な手段の一つである。Further, the catalysts represented by the formulas (1) and (2)
The reaction of the formula (1) may not be performed on the same catalyst surface, and a catalyst that promotes the reaction of the formula (1) and a catalyst that promotes the reaction of the formula (2) may be uniformly mixed. However, in this case, since the heat conduction efficiency is lower than the reaction on the same catalyst, the hydrogen production efficiency slightly decreases, but this is one of effective means.
【００３１】以上のような触媒を用いて、酸素または空
気と炭化水素，水蒸気から水素を高効率で製造すること
ができる。Using the above catalyst, hydrogen can be produced with high efficiency from oxygen or air, hydrocarbons and water vapor.
【００３２】また、前記の式（１）で生成したＣＯも、
以下に示す式（３）のシフト反応により、水素に転換さ
れて水素濃度が高くなる。The CO generated by the above formula (1) is also:
By the shift reaction of the formula (3) shown below, it is converted into hydrogen and the hydrogen concentration increases.
【００３３】[0033]
【化３】 ＣＯ＋Ｈ2Ｏ → ＣＯ2＋Ｈ２ …（３） この場合、通常用いられるＣｕ，Ｃｒ，Ｚｎ等を含むシ
フト触媒が有効である。また、固体高分子形燃料電池用
の水素製造においては、式（３）のシフト反応でＣＯ2
に転換できなかったＣＯは、燃料電池の電極の性能を劣
化させるために、１００ｐｐｍ以下に低減させる必要が
ある。これには、シフト触媒の後段にＣＯ選択酸化触媒
を設置し、酸素または空気を加えてＣＯを選択的に酸化
する。この触媒は通常のＣＯ選択酸化触媒でよい。[Image Omitted] CO + H 2 O → CO 2 + H 2 (3) In this case, a commonly used shift catalyst containing Cu, Cr, Zn or the like is effective. In addition, in the production of hydrogen for a polymer electrolyte fuel cell, CO 2 is produced by the shift reaction of the formula (3).
It is necessary to reduce the CO that could not be converted to 100 ppm or less in order to deteriorate the performance of the electrode of the fuel cell. To this end, a CO selective oxidation catalyst is provided downstream of the shift catalyst, and oxygen or air is added to selectively oxidize CO. The catalyst may be a conventional CO selective oxidation catalyst.
【００３４】本発明において使用する原料の炭化水素
は、ＣＨ4，天然ガス（ＬＮＧ），プロパン，ブタン等
のガス状炭化水素，ナフサ，灯油，ガソリン，軽油等の
液状炭化水素等で、改質反応に比較的高温を必要とする
ものが主な対象である。The hydrocarbons used as raw materials in the present invention are gaseous hydrocarbons such as CH 4 , natural gas (LNG), propane and butane, and liquid hydrocarbons such as naphtha, kerosene, gasoline and light oil, and the like. Those requiring relatively high temperatures for the reaction are the main targets.
【００３５】[0035]
【発明の実施の形態】以下に、本発明の実施例について
説明する。Embodiments of the present invention will be described below.
【００３６】〔実施例 １〕図２は、本実施例の炭化水
素の改質試験を行った試験装置の模式断面図である。本
実施例では、原料の炭化水素としてＣＨ4を用いた。Embodiment 1 FIG. 2 is a schematic cross-sectional view of a test apparatus for performing a hydrocarbon reforming test of this embodiment. In this example, CH 4 was used as a raw material hydrocarbon.
【００３７】反応管１１は電気炉１２で周囲から加熱さ
れるようになっている。反応管１１には触媒１３が充填
されており、触媒１３のガス上流側には、原料ガスが十
分に混合されるように充填材１４が充填されている。触
媒１３のガス出口部には温度センサ１５が設置されてお
り、触媒１３を通過する生成ガスの温度を測定できるよ
うになっている。The reaction tube 11 is heated from the surroundings by an electric furnace 12. The reaction tube 11 is filled with a catalyst 13, and a filler 14 is filled upstream of the catalyst 13 so that the raw material gas is sufficiently mixed. A temperature sensor 15 is provided at the gas outlet of the catalyst 13 so that the temperature of the product gas passing through the catalyst 13 can be measured.
【００３８】初めに、反応管１１に空気を２.９９リッ
トル／ｍｉｎの速度で供給しながら、外周から電気炉１
２で加熱した。温度センサ１５で計測される触媒１３
の、出口におけるガスの温度が１００℃に達したところ
で、反応管１１の上部から水を１.５８ｇ／ｍｉｎの速
度で供給した。First, while supplying air to the reaction tube 11 at a rate of 2.99 l / min, the electric furnace 1
Heated at 2. Catalyst 13 measured by temperature sensor 15
When the gas temperature at the outlet reached 100 ° C., water was supplied from the upper part of the reaction tube 11 at a rate of 1.58 g / min.
【００３９】さらに触媒１３の加熱を続け、温度センサ
１５で計測される触媒１３の出口におけるガスの温度が
４００℃に達した時点で、ＣＨ4を０.７８リットル／ｍ
ｉｎの速度で供給すると同時に、電気炉１２を停止して
外部からの加熱を止めた。When the temperature of the gas at the outlet of the catalyst 13 measured by the temperature sensor 15 reaches 400 ° C., CH 4 is reduced to 0.78 l / m 2.
At the same time, the electric furnace 12 was stopped to stop the external heating.
【００４０】原料の組成は、Ｈ2Ｏ（モル）／ＣＨ4（モ
ル）＝２.５、Ｏ2（モル）／ＣＨ4（モル）＝０.８で、
触媒１３の入口における乾燥ガスベースでの空間速度は
１００００ｈ~1とした。The composition of the raw materials is as follows: H 2 O (mol) / CH 4 (mol) = 2.5, O 2 (mol) / CH 4 (mol) = 0.8,
The space velocity on a dry gas basis at the inlet of the catalyst 13 was set to 10000h- 1 .
【００４１】触媒１３としては、セル数４００セル／ｉ
ｎｃｈ2のコージェライトハニカム構造体にＬａ・β−
Ａｌ2Ｏ3をコーティングした後、Ｐｄをハニカム１リッ
トル当り１.５ｇ、Ｒｕをハニカム１リットル当り１.５
ｇ担持した触媒を用いた。As the catalyst 13, the number of cells was 400 cells / i.
La-β- is added to the cordierite honeycomb structure of nch 2
After coating with Al 2 O 3 , Pd was 1.5 g / l honeycomb and Ru was 1.5 g / l honeycomb.
g supported catalyst was used.
【００４２】図３は、上記の条件で試験した場合の、触
媒１３の出口における生成ガスの温度特性を示すグラフ
である。FIG. 3 is a graph showing the temperature characteristics of the produced gas at the outlet of the catalyst 13 when the test was conducted under the above conditions.
【００４３】生成ガスの温度は、電気炉１２による加熱
に伴い上昇し、１分後には所定の温度である７００℃で
安定した。The temperature of the produced gas rose with the heating by the electric furnace 12, and was stabilized at a predetermined temperature of 700 ° C. after one minute.
【００４４】また、電気炉１２を停止した後も、原料ガ
スの供給を続けている間は、触媒１３の温度はほぼ７０
０℃で一定になっており、熱的に自立していることが分
かった。反応が完全に定常となった時点で出口ガスの分
析を行い、水素生成量を測定した。その結果を表１に示
す。Further, even after the electric furnace 12 is stopped, while the supply of the raw material gas is continued, the temperature of the catalyst 13 becomes approximately 70 ° C.
It was constant at 0 ° C., indicating that it was thermally independent. When the reaction became completely steady, the outlet gas was analyzed and the amount of hydrogen generated was measured. Table 1 shows the results.
【００４５】[0045]
【表１】 [Table 1]
【００４６】表１において、理論計算値は、ＣＨ4，Ｈ2
Ｏ，空気を実施例１の組成、温度で反応させたときの平
衡値である。この結果から、水素は理論計算値に近い値
を示し、本発明が有効であることが分かる。なお、水素
以外のＣＯ，ＣＯ2，ＣＨ4も理論値に近いことがことが
明確である。In Table 1, the theoretical calculation values are CH 4 , H 2
This is an equilibrium value when O and air are reacted at the composition and temperature of Example 1. From these results, hydrogen shows a value close to the theoretical calculation value, which indicates that the present invention is effective. It is clear that CO, CO 2 , and CH 4 other than hydrogen are close to the theoretical values.
【００４７】〔実施例 ２〕図４は、本実施例の炭化水
素の改質試験を行った試験装置の模式断面図である。本
試験装置は、図２に示した試験装置に、反応管１１へ供
給する空気，ＣＨ4および水を予熱するための予熱器１
６を設けた点が特徴である。[Embodiment 2] FIG. 4 is a schematic sectional view of a test apparatus for performing a hydrocarbon reforming test of this embodiment. This test apparatus is different from the test apparatus shown in FIG. 2 in that a preheater 1 for preheating air, CH 4 and water supplied to the reaction tube 11 is provided.
6 is provided.
【００４８】始めに、反応管１１を外周から電気炉１２
で加熱し、温度センサ１５で計測される触媒１３の、出
口におけるガスの温度が４５０℃に達した時点で、予熱
器１６で予め４５０℃に加熱した空気，メタンおよび水
を、それぞれ１.８７リットル／ｍｉｎ、０.７８リット
ル／ｍｉｎ、１.５８ｇ／ｍｉｎの速度で供給した。そ
れと同時に電気炉１２を停止して外部からの加熱を止め
た。First, the reaction tube 11 was moved from the outer periphery to the electric furnace 12.
When the temperature of the gas at the outlet of the catalyst 13 measured by the temperature sensor 15 reaches 450 ° C., the air, methane, and water which have been heated to 450 ° C. Liter / min, 0.78 liter / min, 1.58 g / min. At the same time, the electric furnace 12 was stopped to stop external heating.
【００４９】原料の組成は、Ｈ2Ｏ（モル）／ＣＨ4（モ
ル）＝２.５、Ｏ2（モル）／ＣＨ4（モル）＝０.６で、
触媒１３の入口における乾燥ガスベースでの空間速度は
１００００ｈ~1とした。触媒１３は、モノリシス構造体
としてメタルハニカムを使用し、かつ、活性成分として
は、ハニカム１リットル当りＰｔを２ｇとＮｉを１８ｇ
担持したものを使用した。The composition of the raw materials is as follows: H 2 O (mol) / CH 4 (mol) = 2.5, O 2 (mol) / CH 4 (mol) = 0.6,
The space velocity on a dry gas basis at the inlet of the catalyst 13 was set to 10000h- 1 . The catalyst 13 uses a metal honeycomb as a monolithic structure, and as an active component, 2 g of Pt and 18 g of Ni per liter of honeycomb.
What was carried was used.
【００５０】上記の条件で試験した結果、触媒１３の出
口におけるガスの温度は、電気炉１２による加熱を止め
ても、所望する７００℃で保持されていた。As a result of the test under the above conditions, the gas temperature at the outlet of the catalyst 13 was maintained at the desired 700 ° C. even when the heating by the electric furnace 12 was stopped.
【００５１】また、７００℃で安定するまでに要する時
間は、実施例１よりも短縮されており、担体として熱容
量が小さく、熱伝導性の良いメタルハニカムを使用する
ことにより応答性が向上したことが分かる。The time required to stabilize at 700 ° C. is shorter than that in Example 1, and the responsiveness is improved by using a metal honeycomb having a small heat capacity and good thermal conductivity as a carrier. I understand.
【００５２】触媒温度が定常となった時点で出口ガスの
分析を行った結果を表２に示す。本実施例においても水
素は理論計算値に近い値を示し、本発明が有効であるこ
とが分かる。Table 2 shows the results of analysis of the outlet gas when the catalyst temperature became steady. Also in this example, hydrogen shows a value close to the theoretical calculation value, which indicates that the present invention is effective.
【００５３】[0053]
【表２】 [Table 2]
【００５４】〔実施例 ３〕図５は、本発明による燃料
改質器を含む固体高分子形燃料電池システムの一例を示
す概略フロー図である。Embodiment 3 FIG. 5 is a schematic flow chart showing an example of a polymer electrolyte fuel cell system including a fuel reformer according to the present invention.
【００５５】本実施例では、水素製造の原料としてＬＮ
Ｇを用いた場合について述べる。本システムは、主に、
燃料改質器１、起動用バーナ２、熱交換器３、シフト反
応器４、ＣＯ除去器５、固体高分子形燃料電池６、ボイ
ラ７から構成されている。燃料改質器１には本発明によ
る触媒が充填されている。空気とＬＮＧは熱交換器３を
経由して燃料改質器１に供給されるようになっている。
水はボイラ７で水蒸気に変えられた後、燃料改質器１に
供給されるようになっている。In this embodiment, LN was used as a raw material for hydrogen production.
The case where G is used will be described. This system is mainly
It comprises a fuel reformer 1, a starter burner 2, a heat exchanger 3, a shift reactor 4, a CO remover 5, a polymer electrolyte fuel cell 6, and a boiler 7. The fuel reformer 1 is filled with the catalyst according to the present invention. Air and LNG are supplied to the fuel reformer 1 via the heat exchanger 3.
The water is converted into steam by the boiler 7 and then supplied to the fuel reformer 1.
【００５６】本システムの運転方法について説明する。
まず始めに、所定流量の空気を燃料改質器１の内部へ、
触媒の上流側から供給すると同時に、燃料と燃焼用空気
を起動用バーナ２に供給して点火し、燃焼ガスを発生さ
せ、これを導入することにより触媒を加熱する。An operation method of the present system will be described.
First, a predetermined flow of air is introduced into the fuel reformer 1,
Simultaneously with the supply from the upstream side of the catalyst, the fuel and the combustion air are supplied to the starting burner 2 to ignite and generate combustion gas, which is heated to heat the catalyst.
【００５７】次に、所定流量の水をボイラ７へ供給して
水蒸気に変えた後、触媒の上流側から燃料改質器１へ供
給する。さらに起動用バーナ２により触媒の加熱を続
け、触媒の温度がＬＮＧの着火温度以上になったところ
で、所定流量のＬＮＧを触媒の上流側から燃料改質器１
の内部に供給する。Next, a predetermined flow rate of water is supplied to the boiler 7 and converted into steam, and then supplied to the fuel reformer 1 from the upstream side of the catalyst. Further, the heating of the catalyst is continued by the starting burner 2, and when the temperature of the catalyst becomes equal to or higher than the ignition temperature of LNG, a predetermined flow rate of LNG is supplied from the fuel reformer 1 to the upstream side of the catalyst.
Supply inside.
【００５８】触媒の温度は、ＬＮＧの供給直後にわずか
に低下するものの、ＬＮＧの酸化により発生する反応熱
によって直ちに再び上昇し始める。この温度上昇が始ま
ったところで、起動用バーナ２への燃料と燃焼用空気の
供給を停止し、起動用バーナ２による触媒の加熱を止め
る。Although the temperature of the catalyst slightly decreases immediately after the supply of LNG, it immediately starts to increase again due to the heat of reaction generated by the oxidation of LNG. When the temperature rise starts, the supply of fuel and combustion air to the starting burner 2 is stopped, and the heating of the catalyst by the starting burner 2 is stopped.
【００５９】その後も、燃料改質器１に充填した触媒に
より熱が発生するために温度が下がることはなく、放熱
とバランスして一定の温度で安定化する。燃料改質器１
の温度が定常状態に達したら、熱交換器３の出口のガス
をシフト反応器４へ導入し、シフト反応により水素濃度
を高め、さらに、ＣＯ除去器５へ導入しＣＯを選択的に
酸化してＣＯ濃度を所定の濃度以下とし、これを固体高
分子形燃料電池６へ導入する。Thereafter, the temperature does not decrease because the catalyst filled in the fuel reformer 1 generates heat, and the temperature is stabilized at a constant temperature in balance with the heat radiation. Fuel reformer 1
When the temperature reaches a steady state, the gas at the outlet of the heat exchanger 3 is introduced into the shift reactor 4, the hydrogen concentration is increased by the shift reaction, and the gas is introduced into the CO remover 5 to selectively oxidize CO. The CO concentration is set to a predetermined concentration or less, and the CO concentration is introduced into the polymer electrolyte fuel cell 6.
【００６０】燃料改質器１の温度の制御は、従来はＬＮ
Ｇと空気と水の供給量を個別に調節していたため、運転
制御が非常に複雑であったが、本発明によれば、ＬＮＧ
と空気と水の組成は変えず、総量の増減により容易に行
うことができる。Conventionally, the temperature of the fuel reformer 1 is controlled by LN
The operation control was very complicated because the supply amounts of G, air, and water were individually adjusted, but according to the present invention, LNG
It can be easily performed by changing the total amount without changing the composition of air and water.
【００６１】例えば、冷起動時は短時間で定常温度に到
達するように原料ガスの量を増やし、温度が定常に近づ
くに伴ない所定量まで減らすようにする。また、外気温
の経日変化や経年変化による装置からの放熱量の変動
も、改質温度に影響を与えるが、そのような場合にも原
料ガスの組成は変えず、総量の増減により容易に所定の
定常温度に調整することができる。For example, at the time of the cold start, the amount of the source gas is increased so as to reach the steady temperature in a short time, and is reduced to a predetermined amount as the temperature approaches the steady state. Fluctuations in the amount of heat radiated from the device due to aging and aging of the outside air temperature also affect the reforming temperature, but in such a case, the composition of the raw material gas does not change, and it is easier to increase or decrease the total amount. It can be adjusted to a predetermined steady temperature.
【００６２】負荷変動に合わせて水素製造量を変える場
合、従来は、ＬＮＧと空気と水の供給量をそれぞれ独立
して調整していたため、水素製造量を変えようとしたと
きに同時に温度が変動しないよう複雑な制御が必要であ
った。しかし、本発明によれば原料ガスの総量を変える
だけで水素製造量を変えることができ、また、このとき
に温度変化が伴わないために、運転制御が著しく容易に
なる。In the case where the hydrogen production amount is changed in accordance with the load fluctuation, conventionally, the supply amounts of LNG, air, and water were independently adjusted. A complicated control was needed to avoid this. However, according to the present invention, the hydrogen production amount can be changed only by changing the total amount of the raw material gas, and at this time, since the temperature does not change, the operation control becomes extremely easy.
【００６３】[0063]
【発明の効果】本発明によれば、ＬＮＧや灯油を原料と
して水素を製造する燃料電池用の燃料改質方法におい
て、従来よりも負荷追従性が著しく改善され、家庭用燃
料電池システムや自動車用燃料電池システム等の高速起
動が要求される装置への用途の拡大を図ることができ
る。According to the present invention, in a fuel reforming method for a fuel cell for producing hydrogen from LNG or kerosene as a raw material, the load following ability is remarkably improved as compared with the conventional method, and the fuel cell system for home use and the automotive fuel cell are used. It is possible to expand applications to devices that require high-speed startup such as a fuel cell system.
【００６４】また、制御用補機の削減、低コスト材料の
使用、構造の簡略化などを図ることができる。Further, it is possible to reduce the number of control auxiliary machines, use low-cost materials, simplify the structure, and the like.
【図１】触媒上での反応の模式図である。FIG. 1 is a schematic diagram of a reaction on a catalyst.
【図２】実施例１の炭化水素の改質試験を行った試験装
置の模式断面図である。FIG. 2 is a schematic cross-sectional view of a test apparatus for performing a hydrocarbon reforming test of Example 1.
【図３】実施例１の触媒の性能を示すグラフである。FIG. 3 is a graph showing the performance of the catalyst of Example 1.
【図４】実施例２の炭化水素の改質試験を行った試験装
置の模式断面図である。FIG. 4 is a schematic cross-sectional view of a test device for performing a hydrocarbon reforming test of Example 2.
【図５】本発明による燃料改質器を含む固体高分子形燃
料電池システムの一例を示す概略フロー図である。FIG. 5 is a schematic flow chart showing an example of a polymer electrolyte fuel cell system including a fuel reformer according to the present invention.
１…燃料改質器、２…起動用バーナ、３…熱交換器、４
…シフト反応器、５…ＣＯ除去器、６…固体高分子形燃
料電池、７…ボイラ、１１…反応管、１２…電気炉、１
３…触媒、１４…充填材、１５…温度センサ、１６…予
熱器。DESCRIPTION OF SYMBOLS 1 ... Fuel reformer, 2 ... Burner for starting, 3 ... Heat exchanger, 4
... Shift reactor, 5 ... CO remover, 6 ... Polymer fuel cell, 7 ... Boiler, 11 ... Reaction tube, 12 ... Electric furnace, 1
3 ... catalyst, 14 ... filler, 15 ... temperature sensor, 16 ... preheater.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｍ 8/10 Ｈ０１Ｍ 8/10 (72)発明者 吉田 紀子 茨城県日立市大みか町七丁目２番１号 株 式会社日立製作所電力・電機開発研究所内 (72)発明者 山下 寿生 茨城県日立市大みか町七丁目２番１号 株 式会社日立製作所電力・電機開発研究所内 (72)発明者 河崎 照文 茨城県日立市大みか町七丁目２番１号 株 式会社日立製作所電力・電機開発研究所内 Ｆターム(参考） 4G040 EA03 EA06 EA07 EB31 EB32 EC02 EC03 EC04 EC07 4G069 AA03 AA08 BA01A BA01B BA13A BA13B BB04A BC16A BC31A BC32A BC35A BC38A BC42A BC42B BC58A BC66A BC67A BC68A BC68B BC70A BC70B BC71A BC72A BC72B BC75A BC75B CC17 DA06 EA19 EC22X EC22Y FA02 FA03 FB23 FC08 4G140 EA03 EA06 EA07 EB31 EB32 EC02 EC03 EC04 EC07 5H026 AA06 5H027 AA06 BA01 BA17 Continued on the front page (51) Int.Cl. 7 Identification FI FI Theme Court II (Reference) H01M 8/10 H01M 8/10 (72) Inventor Noriko Yoshida 7-2-1, Omikacho, Hitachi City, Hitachi City, Ibaraki Pref. Within the Hitachi, Ltd. Power and Electricity Development Laboratory (72) Inventor Toshio Yamashita 7-2-1, Omika-cho, Hitachi, Ibaraki Prefecture Within the Hitachi, Ltd. Power and Electricity Development Laboratory (72) Inventor Teruhumi Kawasaki Hitachi, Ibaraki 7-2-1, Omikacho F-term in Hitachi, Ltd. Electric Power and Electric Power Development Laboratory Co., Ltd. BC66A BC67A BC68A BC68B BC70A BC70B BC71A BC72A BC72B BC75A BC75B CC17 DA06 EA19 EC22X EC22Y FA02 FA03 FB23 FC08 4G140 EA03 EA06 EA07 EB31 EB32 EC02 EC03 EC04 EC07 5H026 AA06 5H027 AA01 BA01 BA01
Claims (6)
む原料ガスを、前記炭化水素の酸化反応および前記炭化
水素の水蒸気改質反応を同時に促進する活性成分を有す
る触媒と接触させることにより、外部から熱を与えずに
水素を製造する燃料改質方法であって、 前記触媒として、少なくともＡｌを含む酸化物で構成さ
れた多孔質担体に、Ｐｄ，Ｐｔ，Ｒｕ，Ｒｈの貴金属お
よび／または前記貴金属とＮｉ，Ｃｏ，Ｆｅ，Ａｇ，Ｃ
ｕ，Ｚｎ，Ｃｒ，希土類の少なくとも１種を担持した触
媒を用い、 前記炭化水素の酸化反応を促進する活性成分と、前記炭
化水素の水蒸気改質活性を促進する活性成分の担持量を
調整して、酸化反応の発熱量と水蒸気改質反応の吸熱量
をバランスさせ、触媒全体を所望の温度に維持すること
を特徴とする燃料改質方法。1. An external gas by contacting a raw material gas containing oxygen or air with hydrocarbons and steam with a catalyst having an active component which simultaneously promotes the oxidation reaction of the hydrocarbons and the steam reforming reaction of the hydrocarbons. A fuel reforming method for producing hydrogen without applying heat from a precious metal such as Pd, Pt, Ru, Rh and / or a porous carrier composed of an oxide containing at least Al as the catalyst. Precious metals and Ni, Co, Fe, Ag, C
A catalyst carrying at least one of u, Zn, Cr, and rare earths is used, and the amount of the active component that promotes the oxidation reaction of the hydrocarbon and the amount of the active component that promotes the steam reforming activity of the hydrocarbon are adjusted. Wherein the calorific value of the oxidation reaction and the endothermic amount of the steam reforming reaction are balanced to maintain the entire catalyst at a desired temperature.
て、希土類・β−アルミナ、または、Ｌａ・β−アルミ
ナを用いた請求項１に記載の燃料改質方法。2. The fuel reforming method according to claim 1, wherein a rare earth β-alumina or La β-alumina is used as the porous carrier for supporting the catalyst.
ジェライトまたはムライトのセラミックスおよび／また
は金属からなるモノリシス構造体を用いた請求項１に記
載の燃料改質方法。3. The fuel reforming method according to claim 1, wherein a monolithic structure made of cordierite or mullite ceramics and / or metal is used as a carrier for supporting the catalyst.
担持した炭化水素酸化触媒とセラミックス製の担体にＮ
ｉ，Ｃｏ，Ｆｅ，Ａｇ，Ｃｕ，Ｚｎ，Ｃｒ，希土類の少
なくとも１種を担持した水蒸気改質触媒を均一に混合し
て形成した触媒を用いる請求項１に記載の燃料改質方
法。4. A hydrocarbon oxidation catalyst comprising a porous carrier carrying a noble metal and a ceramic carrier comprising N
The fuel reforming method according to claim 1, wherein a catalyst formed by uniformly mixing a steam reforming catalyst supporting at least one of i, Co, Fe, Ag, Cu, Zn, Cr, and rare earth is used.
応させるシフト反応触媒およびＣＯをＣＯ2に選択的に
酸化する触媒を設置した請求項１に記載の燃料改質方
法。5. The fuel reforming method according to claim 1, wherein a shift reaction catalyst for reacting CO with H 2 O and a catalyst for selectively oxidizing CO to CO 2 are provided downstream of the fuel reformer.
む原料ガスをコージェライト，ムライトのセラミックス
および／または金属からなるモノリシス構造体に、Ｌａ
・β−アルミナ多孔質担体をコーティングし、かつ、Ｐ
ｄ，Ｐｔ，Ｒｕ，Ｒｈの貴金属および／または前記貴金
属とＮｉ，Ｃｏ，Ｆｅ，Ａｇ，Ｃｕ，Ｚｎ，Ｃｒ，希土
類の少なくとも１種を担持した触媒と接触させることに
より、前記炭化水素の酸化反応および水蒸気改質反応を
同時に促進させ、外部から熱を与えずに水素を製造する
ことを特徴とする燃料改質方法。6. A monolithic structure made of ceramics and / or metal of cordierite or mullite is converted into a raw material gas containing oxygen or air, a hydrocarbon, and water vapor.
.Beta.-alumina porous carrier is coated and P
d. Pt, Ru, Rh noble metal and / or the noble metal is brought into contact with a catalyst supporting at least one of Ni, Co, Fe, Ag, Cu, Zn, Cr, and rare earths, thereby oxidizing the hydrocarbon. And a steam reforming reaction at the same time to produce hydrogen without externally applying heat.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000299102A JP2002104808A (en) | 2000-09-27 | 2000-09-27 | Method of reforming fuel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000299102A JP2002104808A (en) | 2000-09-27 | 2000-09-27 | Method of reforming fuel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002104808A true JP2002104808A (en) | 2002-04-10 |
| JP2002104808A5 JP2002104808A5 (en) | 2005-08-25 |
Family
ID=18780959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000299102A Pending JP2002104808A (en) | 2000-09-27 | 2000-09-27 | Method of reforming fuel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002104808A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004002186A (en) * | 2002-05-13 | 2004-01-08 | Boc Group Inc:The | Gas recovery method |
| JP2005537132A (en) * | 2002-08-26 | 2005-12-08 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Multilayer catalyst for self-heat exchange steam reforming of hydrocarbons and process using said catalyst |
| JP2006036567A (en) * | 2004-07-26 | 2006-02-09 | T Rad Co Ltd | Steam reforming method and mixed catalyst |
| WO2007029862A1 (en) * | 2005-09-08 | 2007-03-15 | Jgc Corporation | Catalyst for catalytic partial oxidation of hydrocarbon and process for producing synthesis gas |
| KR100700552B1 (en) | 2005-10-11 | 2007-03-28 | 엘지전자 주식회사 | Catalyst charging method of reformer for fuel cell |
| JP2007117798A (en) * | 2005-10-25 | 2007-05-17 | Ishikawajima Harima Heavy Ind Co Ltd | Reforming catalyst, reforming method, operation method and structure of reforming catalyst |
| JP2008189540A (en) * | 2007-01-12 | 2008-08-21 | Tdk Corp | Oxygen permeable membrane and system for generating hydrogen |
| WO2009054830A1 (en) * | 2007-10-25 | 2009-04-30 | Utc Power Corporation | Reduced generation of ammonia in nickel catalyst of reformer |
-
2000
- 2000-09-27 JP JP2000299102A patent/JP2002104808A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004002186A (en) * | 2002-05-13 | 2004-01-08 | Boc Group Inc:The | Gas recovery method |
| JP2005537132A (en) * | 2002-08-26 | 2005-12-08 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Multilayer catalyst for self-heat exchange steam reforming of hydrocarbons and process using said catalyst |
| JP2006036567A (en) * | 2004-07-26 | 2006-02-09 | T Rad Co Ltd | Steam reforming method and mixed catalyst |
| WO2007029862A1 (en) * | 2005-09-08 | 2007-03-15 | Jgc Corporation | Catalyst for catalytic partial oxidation of hydrocarbon and process for producing synthesis gas |
| KR100700552B1 (en) | 2005-10-11 | 2007-03-28 | 엘지전자 주식회사 | Catalyst charging method of reformer for fuel cell |
| JP2007117798A (en) * | 2005-10-25 | 2007-05-17 | Ishikawajima Harima Heavy Ind Co Ltd | Reforming catalyst, reforming method, operation method and structure of reforming catalyst |
| JP2008189540A (en) * | 2007-01-12 | 2008-08-21 | Tdk Corp | Oxygen permeable membrane and system for generating hydrogen |
| WO2009054830A1 (en) * | 2007-10-25 | 2009-04-30 | Utc Power Corporation | Reduced generation of ammonia in nickel catalyst of reformer |
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