JP4872204B2 - Reformer for hydrogen production - Google Patents
Reformer for hydrogen production Download PDFInfo
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- JP4872204B2 JP4872204B2 JP2004284226A JP2004284226A JP4872204B2 JP 4872204 B2 JP4872204 B2 JP 4872204B2 JP 2004284226 A JP2004284226 A JP 2004284226A JP 2004284226 A JP2004284226 A JP 2004284226A JP 4872204 B2 JP4872204 B2 JP 4872204B2
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- 239000001257 hydrogen Substances 0.000 title claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 claims 2
- 230000003647 oxidation Effects 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Classifications
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- 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
Description
本発明は、水素製造用改質器に関する。 The present invention relates to a reformer for hydrogen production.
水素製造用改質器（以下単に改質器ともいう）の構成部品（改質器部材）は大きな伝熱容量を確保するために、できるだけ薄板にすることが求められている。しかしながら、こうした構成部材などは、板厚が薄くなればなるほど繰り返し酸化に伴うスケール剥離に起因する特性の低下と耐用期間の縮減を招くことになる。このような背景のもとに、かかる改質器部材には、従来一般にＳＵＳ３０４およびＳＵＳ３１６Ｌのステンレス鋼が採用され、また、これらの材料で耐用不十分な場合はＳＵＳ３１０Ｓや特許文献１記載のフェライト系ステンレス鋼が使用されている。
しかし、上記ＳＵＳ３０４、ＳＵＳ３１６Ｌ（オーステナイト系ステンレス鋼）では、スケールがスポーリング（剥離）して板厚減少が大きく高温での使用に難点がある。また、水蒸気の添加された高温雰囲気では、さらにオーステナイト系ステンレス鋼の中でも材料グレードの高いＳＵＳ３１０Ｓや特許文献１記載のフェライト系ステンレス鋼でも同様の現象が発生する。また、改質器では、運転時に部位間に温度差が生じ、該温度差によって熱歪みが生じて、割れが発生する問題がある。この点、オーステナイト系ステンレス鋼は熱膨張率が高く、割れに対しては不利となる。 However, the above SUS304 and SUS316L (austenitic stainless steel) have a difficulty in use at high temperatures because the scale is spalled (peeled) and the plate thickness is greatly reduced. Further, in a high temperature atmosphere to which water vapor is added, the same phenomenon occurs even in SUS310S having a high material grade and ferritic stainless steel described in Patent Document 1 among austenitic stainless steels. Further, the reformer has a problem in that a temperature difference is generated between parts during operation, a thermal strain is generated due to the temperature difference, and a crack is generated. In this respect, austenitic stainless steel has a high coefficient of thermal expansion, which is disadvantageous for cracking.
そこで、本発明は、４００℃以上の高温あるいはさらに水蒸気添加雰囲気で高温酸化による腐食、減肉を生じにくいフェライト系ステンレス鋼を用いた水素製造用改質器を提供することを目的とする。 Accordingly, an object of the present invention is to provide a reformer for hydrogen production using a ferritic stainless steel which is unlikely to cause corrosion or thinning due to high temperature oxidation in a high temperature of 400 ° C. or higher or further in a steam addition atmosphere.
前記目的を達成した本発明は、（１）使用温度が４００℃以上で緻密なアルミナ被膜を形成しかつ水蒸気含有ガスと接触する部分を含む改質器部材にＡｌ：１．０〜８．０ｍａｓｓ％およびＬａ：０．０１０〜０．１５０ｍａｓｓ％を含有するフェライト系ステンレス鋼を用いて構成されたことを特徴とする水素製造用改質器であり、また、（２）使用温度が５５０℃以上で緻密なアルミナ被膜を形成しかつ水蒸気含有ガスと接触する部分を含む改質器部材にＡｌ：１．０〜８．０ｍａｓｓ％およびＬａ：０．０１０〜０．１５０ｍａｓｓ％を含有するフェライト系ステンレス鋼を用いて構成されたことを特徴とする水素製造用改質器である。
The present invention that has achieved the above object is as follows : ( 1 ) Al: 1.0 to 8.0 mass in a reformer member that includes a portion that forms a dense alumina coating at a use temperature of 400 ° C. or higher and that contacts a steam-containing gas. % And La: a reformer for producing hydrogen characterized by using ferritic stainless steel containing 0.010 to 0.150 mass%, and ( 2 ) a use temperature of 550 ° C. or higher. Ferritic stainless steel containing Al: 1.0 to 8.0 mass% and La: 0.010 to 0.150 mass% in a reformer member that includes a portion that forms a dense alumina coating and is in contact with a steam-containing gas This is a reformer for hydrogen production, characterized by comprising steel.
本発明によれば、４００℃以上、さらには５５０℃以上の高温環境で、水蒸気含有ガスにさらされても、異常酸化による崩壊がなく、熱応力による割れ発生も起こらない部材より構成された水素製造用改質器が得られる。 According to the present invention, hydrogen is composed of a member that does not collapse due to abnormal oxidation and does not cause cracking due to thermal stress even when exposed to a water vapor-containing gas in a high temperature environment of 400 ° C. or higher, further 550 ° C. or higher. A production reformer is obtained.
本発明に係る水素製造用改質器では、改質器部材のうち使用温度が４００℃以上になる部分を含むものは、Ａｌ：１．０〜８．０ｍａｓｓ％を含有するフェライト系ステンレス鋼であることが必要であり、Ａｌ以外の成分については、フェライト系ステンレス鋼から逸脱しない範囲で適宜の元素を適宜の量添加してもよい。例えばＪＩＳ Ｇ ４３０４，４３０５に規定するフェライト系ステンレス鋼である。例えば酸化被膜の密着性を良くするためにＬａを適量添加してもよい。Ｌａ添加量は０．０１０ｍａｓｓ％以上０．１５０ｍａｓｓ％以下が密着性の点から好ましい。特に、使用温度が５５０℃以上になる部分あるいは水蒸気含有ガスと接触する部分を有する構成部材に上記組成のフェライト系ステンレス鋼を用いた場合には、本発明の効果（他の材料を用いた場合との効果の差）がより顕著に現れる。なお、ここでいう水蒸気含有ガスとは、メタン、プロパン等の炭化水素ガス主体のガス（天然ガスまたは都市ガスも含む）と水蒸気との混合ガスを指す。また、酸化増量の観点から、Ａｌは３．０ｍａｓｓ％以上が好ましい。 In the reformer for hydrogen production according to the present invention, the reformer member including the portion where the operating temperature is 400 ° C. or more is ferritic stainless steel containing Al: 1.0 to 8.0 mass%. It is necessary that a component other than Al may be added in an appropriate amount within a range not departing from the ferritic stainless steel. For example, it is a ferritic stainless steel specified in JIS G 4304 and 4305. For example, an appropriate amount of La may be added to improve the adhesion of the oxide film. The La addition amount is preferably 0.010 mass% or more and 0.150 mass% or less from the viewpoint of adhesion. In particular, when the ferritic stainless steel having the above composition is used for a constituent member having a portion where the operating temperature is 550 ° C. or higher or a portion in contact with the water vapor-containing gas, the effect of the present invention (when other materials are used) The difference in the effect) appears more prominently. The water vapor-containing gas here refers to a mixed gas of water (including natural gas or city gas) mainly composed of hydrocarbon gas such as methane and propane, and water vapor. Further, from the viewpoint of increasing the amount of oxidation, Al is preferably 3.0 mass% or more.
２０ｍａｓｓ％Ｃｒ-５ｍａｓｓ％Ａｌ（-０．０８０ｍａｓｓ％Ｌａ添加）含有フェライト系ステンレス鋼（本発明用鋼Ａという）、ＳＵＳ３０４、ＳＵＳ３１６ＬおよびＳＵＳ３１０Ｓ（後三者はいずれもＡｌ：１．０ｍａｓｓ％未満）の鋼板試料をそれぞれ９００℃-３０ｖｏｌ.％水蒸気雰囲気で酸化テストした際の各材料表面の耐酸化性を図２に示す。酸化の進展度合いは酸化増量で評価した。酸化が進むと鋼が酸素と結合して重量が増加するので酸化増量にて材料および部材の耐酸化性が評価できる。本発明用鋼Ａが格段に優れた耐酸化性を示すことがわかる。 20 mass% Cr-5 mass% Al (-0.080 mass% La added) ferritic stainless steel (referred to as steel A for the present invention), SUS304, SUS316L and SUS310S (the latter three are all less than Al: 1.0 mass%) FIG. 2 shows the oxidation resistance of the surface of each material when the steel plate samples were subjected to an oxidation test in a water vapor atmosphere at 900 ° C.-30 vol.%. The progress of oxidation was evaluated by oxidation increase. As the oxidation progresses, the steel is combined with oxygen and the weight increases. Therefore, the oxidation resistance of the material and the member can be evaluated by increasing the amount of oxidation. It turns out that steel A for this invention shows the oxidation resistance which was outstandingly excellent.
また、１１００℃×３００ｈで酸化テストした材料表層部を顕微鏡で調べたところ、本発明用鋼Ａは緻密なアルミナ（Ａｌ２Ｏ３）被膜を形成して酸化を抑制した（図３参照）のに対し、オーステナイト系の中でも耐熱性に優れるＳＵＳ３１０Ｓでさえも結晶粒界が侵食されスケールが剥離していた（図４参照）。 Moreover, when the surface layer part of the material subjected to the oxidation test at 1100 ° C. × 300 h was examined with a microscope, the steel A for the present invention formed a dense alumina (Al 2 O 3 ) film to suppress oxidation (see FIG. 3). On the other hand, even in SUS310S, which is excellent in heat resistance among austenite series, the grain boundaries were eroded and the scale was peeled off (see FIG. 4).
本発明用鋼のＡｌ量を１．０〜８．０ｍａｓｓ％とした理由は、１．０ｍａｓｓ％未満では緻密なアルミナ被膜が形成されずに、（ＦｅＣｒ）２Ｏ被膜ができて酸化を充分に抑制することができず（図５参照）、一方、８．０ｍａｓｓ％を超えると熱延板の靭性が著しく低下（図６参照）して製造ラインに通板することができないからである。 The reason why the amount of Al in the steel for use in the present invention is 1.0 to 8.0 mass% is that if it is less than 1.0 mass%, a dense alumina coating is not formed, and a (FeCr) 2 O coating is formed to sufficiently oxidize. On the other hand, if it exceeds 8.0 mass%, the toughness of the hot-rolled sheet is remarkably lowered (see FIG. 6) and cannot be passed through the production line.
図１に示す一般家庭用の固体高分子形燃料電池（ＰＥＦＣ）１において、使用時に少なくとも一部が４００℃以上になる改質器２の構成部材として前記本発明用鋼Ａの板（最小板厚＝０．４ｍｍ、最大板厚＝３．０ｍｍ）を使用し、本発明例とした。この改質器の運転条件は、都市ガス組成＝２０ｖｏｌ．％水蒸気-ＣＨ４-Ｈ２‐ＣＯ‐ＣＯ２、都市ガス供給流量＝０．８ｍ３（標準状態）/ｈ、排気ガス組成＝２５ｖｏｌ．％水蒸気-ＣＯ２‐Ｏ２‐Ｎ２とした。また、５０μｍ、１００μｍ等の厚みの部材にも適応ができる。
In the general polymer electrolyte fuel cell (PEFC) 1 shown in FIG. 1, the steel A plate (minimum plate) of the present invention is used as a component of the
また、比較例１〜３として、上記本発明例において本発明用鋼Ａに代えてＳＵＳ３０４（１８Ｃｒ‐０．００２Ａｌ）、ＳＵＳ３１６Ｌ（１７Ｃｒ‐０．００５Ａｌ）、ＳＵＳ３１０Ｓ（２４Ｃｒ‐０．０１０Ａｌ）をそれぞれ用いた以外は同様に構成した改質器を、上記本発明例と同一条件で運転した。 As Comparative Examples 1 to 3, SUS304 (18Cr-0.002Al), SUS316L (17Cr-0.005Al), and SUS310S (24Cr-0.010Al) are used instead of the steel A for the present invention in the above-described inventive examples. A reformer configured in the same manner except that it was used was operated under the same conditions as in the above-described example of the present invention.
その結果、図２のように改質器の寿命は、比較例１（ＳＵＳ３０４）、２（ＳＵＳ３１６Ｌ）、３（ＳＵＳ３１０Ｓ）ではそれぞれ６００ｈ、９００ｈ、１５００ｈであったのに対し、本発明例では４００００ｈまで延長できた。 As a result, as shown in FIG. 2, the life of the reformer was 600 h, 900 h, and 1500 h in Comparative Example 1 (SUS304), 2 (SUS316L), and 3 (SUS310S), respectively, whereas 40000 h in the present invention example. We were able to extend to.
なお、本発明は、固体酸化物形燃料電池（ＳＯＦＣ）の改質器に適用した場合にも、同様の効果が得られる。 The same effect can be obtained when the present invention is applied to a reformer of a solid oxide fuel cell (SOFC).
本発明は、燃料電池の製造に利用することができる。 The present invention can be used for manufacturing a fuel cell.
１ 一般家庭用ＰＥＦＣ
２ 改質器（水素製造用改質器）
３ 発電部品
1 PEFC for general household
2 Reformer (reformer for hydrogen production)
3 Power generation parts
Claims (2)
Al: 1.0 to 8.0 mass% and La: 0.010 to 0.150 mass% for the reformer member that includes a portion that forms a dense alumina coating at a use temperature of 550 ° C. or higher and is in contact with the steam-containing gas. A reformer for producing hydrogen, characterized in that it is made of a ferritic stainless steel containing iron.
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| JP4872204B2 true JP4872204B2 (en) | 2012-02-08 |
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| JP2006236600A (en) * | 2005-02-22 | 2006-09-07 | Jfe Steel Kk | Solid oxide fuel cell |
| JP4987375B2 (en) * | 2006-07-26 | 2012-07-25 | 株式会社東芝 | Hydrogen production system and method |
| JP5646370B2 (en) * | 2011-03-02 | 2014-12-24 | 東芝燃料電池システム株式会社 | Fuel processing apparatus, fuel cell power generation system and operation method thereof |
| JP5860099B2 (en) * | 2014-06-19 | 2016-02-16 | 株式会社Ｔｉ | Hydrogen generator |
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| JPS5725386A (en) * | 1980-07-23 | 1982-02-10 | Jgc Corp | Carbon deposition-preventing apparatus |
| US6559094B1 (en) * | 1999-09-09 | 2003-05-06 | Engelhard Corporation | Method for preparation of catalytic material for selective oxidation and catalyst members thereof |
| JP3886785B2 (en) * | 2001-11-22 | 2007-02-28 | 日新製鋼株式会社 | Ferritic stainless steel for petroleum fuel reformers |
| JP3910419B2 (en) * | 2001-11-22 | 2007-04-25 | 日新製鋼株式会社 | Ferritic stainless steel for alcohol fuel reformers |
| JP3942876B2 (en) * | 2001-11-22 | 2007-07-11 | 日新製鋼株式会社 | Ferritic stainless steel for hydrocarbon fuel reformer |
| JP2003286005A (en) * | 2002-03-28 | 2003-10-07 | Nisshin Steel Co Ltd | Fuel reformer |
| JP4127685B2 (en) * | 2004-08-30 | 2008-07-30 | 株式会社東芝 | Carbon monoxide selective methanator, carbon monoxide shift reactor and fuel cell system |
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