JP2004097870A - Adsorbent for removing sulfur compound and manufacturing method for hydrogen for fuel cell - Google Patents
Adsorbent for removing sulfur compound and manufacturing method for hydrogen for fuel cell Download PDFInfo
- Publication number
- JP2004097870A JP2004097870A JP2002259768A JP2002259768A JP2004097870A JP 2004097870 A JP2004097870 A JP 2004097870A JP 2002259768 A JP2002259768 A JP 2002259768A JP 2002259768 A JP2002259768 A JP 2002259768A JP 2004097870 A JP2004097870 A JP 2004097870A
- Authority
- JP
- Japan
- Prior art keywords
- adsorbent
- hydrocarbon
- containing gas
- oxide
- oxides
- 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.)
- Granted
Links
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
- Fuel Cell (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、硫黄化合物除去用吸着剤及び燃料電池用水素の製造方法に関し、さらに詳しくは、炭化水素含有ガス中の硫黄分を、室温においても低濃度まで効率よく除去し得る硫黄化合物除去用吸着剤、及び上記吸着剤を用いて脱硫処理した炭化水素含有ガスから、燃料電池用水素を効果的に製造する方法に関する。
【０００２】
【従来の技術】
ＬＰＧや都市ガスなどを改質して燃料電池用水素を製造する場合、改質触媒の被毒を抑制するためには、ガス中の硫黄分を０．０１ｐｐｍ以下に低減させることが要求される。また、プロピレンやブテンなどは、石油化学製品の原料として使用する場合、やはり触媒の被毒を防ぐためには、硫黄分を０．０１ｐｐｍ以下に低減させることが要求される。
前記ＬＰＧ中には、硫黄化合物として、一般にメチルメルカプタンや硫化カルボニル（ＣＯＳ）などに加えて、着臭剤として添加されたジメチルサルファイド（ＤＭＳ）、ｔ−ブチルメルカプタン（ＴＢＭ）、メチルエチルサルファイドなどが含まれている。このようなＬＰＧなどの燃料ガス中の硫黄分を吸着除去するための各種吸着剤が知られている。しかしながら、これらの吸着剤は、１５０〜３００℃程度では高い脱硫性能を示すものがあるが、常温での脱硫性能については、必ずしも充分に満足し得るものではないのが実状であった。
【０００３】
例えば、疎水性ゼオライトにＡｇ，Ｃｕ、Ｚｎ、Ｆｅ、Ｃｏ、Ｎｉなどをイオン交換により担持させた脱硫剤（例えば特許文献１参照）や、Ｙ型ゼオライト、β型ゼオライト又はＸ型ゼオライトにＡｇ又はＣｕを担持した脱硫剤（例えば、特許文献２参照）が開示されている。しかしながら、これらの脱硫剤は、メルカプタン類やサルファイド類を室温において効率的に吸着除去し得るものの、硫化カルボニルをほとんど吸着しないことがわかった。
また、銅−亜鉛系脱硫剤が開示されている（例えば、特許文献３参照）。しかしながら、この脱硫剤においては、１５０℃以上の温度ではＣＯＳを含む各種硫黄化合物を吸着除去できるが、１００℃以下の低い温度では、硫黄化合物に対する吸着性能が低い。さらに、アルミナなどの多孔質担体に銅を担持した脱硫剤が開示されている（例えば、特許文献４参照）。この脱硫剤は１００℃以下の温度でも使用できるとしているが、その吸着性能については十分に満足し得るものではない。
【０００４】
【特許文献１】
特開２００１−２８６７５３号公報
【特許文献２】
特開２００１−３０５１２３号公報
【特許文献３】
特開平２−３０２４９６号公報（第２頁）
【特許文献４】
特開２００１−１２３１８８号公報（第３頁）
【０００５】
【発明が解決しようとする課題】
本発明は、このような状況下で、炭化水素含有ガス中の硫黄分を、室温においても低濃度まで効率よく除去し得る硫黄化合物除去用吸着剤、及び上記吸着剤を用いて脱硫処理した炭化水素含有ガスから、燃料電池用水素を効果的に製造する方法を提供することを目的とするものである。
【０００６】
【課題を解決するための手段】
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、特定の金属酸化物を含む担体に、ある種の金属やその酸化物を担持したものが、硫黄化合物除去用吸着剤としてその目的に適合し得ること、そしてこの吸着剤を用いて脱硫処理した炭化水素含有ガスを改質処理することにより、燃料電池用水素が効果的に得られることを見出した。本発明は、かかる知見に基づいて完成したものである。
すなわち、本発明は、
（１）周期表第３族に属する金属元素の酸化物を含む担体に、銀及びその酸化物並びに銅及びその酸化物の中から選ばれる少なくとも一種を担持させてなる、炭化水素含有ガス中の硫黄化合物除去用吸着剤、
（２）周期表第３族に属する金属元素の酸化物が、Ｌａ、Ｃｅ、Ｓｃ、Ｙ、Ｎｄ、Ｐｒ、Ｓｍ、Ｇｄ及びＹｂの中から選ばれる少なくとも一種の金属の酸化物である上記（１）の炭化水素含有ガス中の硫黄化合物除去用吸着剤、
（３）周期表第３族に属する金属元素の酸化物が、Ｌａ、Ｙｂ、Ｙ及びＣｅの中から選ばれる少なくとも一種の金属の酸化物である上記（２）の炭化水素含有ガス中の硫黄化合物除去用吸着剤、
（４）炭化水素含有ガスが、ＬＰＧ、都市ガス、天然ガス、又はエタン、エチレン、プロパン、プロピレン及びブタンの中から選ばれる少なくとも一種を含むガスである上記（１）〜（３）の炭化水素含有ガス中の硫黄化合物除去用吸着剤、
（５）銀及びその酸化物並びに銅及びその酸化物の中から選ばれる少なくとも一種の担持量が、金属として、吸着剤全量に基づき１〜５０質量％である上記（１）〜（４）の炭化水素含有ガス中の硫黄化合物除去用吸着剤、
（６）銀及びその酸化物並びに銅及びその酸化物の中から選ばれる少なくとも一種の担持量が、金属として、吸着剤全量に基づき３〜３０質量％である請求項５記載の炭化水素含有ガス中の硫黄化合物除去用吸着剤、
（７）周期表第３族に属する金属元素の酸化物の含有量が５〜９９質量％である上記（１）〜（６）の炭化水素含有ガス中の硫黄化合物除去用吸着剤、
（８）上記（１）〜（７）の吸着剤を用いて、炭化水素含有ガス中の硫黄化合物を脱硫処理したのち、脱硫処理炭化水素含有ガスを部分酸化触媒、オートサーマル改質触媒又は水蒸気改質触媒と接触させることを特徴とする燃料電池用水素の製造方法、及び
（９）部分酸化触媒、オートサーマル改質触媒又は水蒸気改質触媒がルテニウム系又はニッケル系触媒である上記（８）の燃料電池用水素の製造方法、
を提供するものである。
【０００７】
【発明の実施の形態】
本発明の硫黄化合物吸着剤は、周期表第３族に属する金属元素の酸化物を含む担体に、活性金属種を担持させたものであり、そして該活性金属種として、銀及びその酸化物並びに銅及びその酸化物の中から選ばれる少なくとも一種が用いられる。
当該吸着剤においては、前記活性金属種の含有量は、金属（銀及び／又は銅）として、１〜５０質量％の範囲が好ましい。この活性金属種の含有量が１質量％未満では十分な脱硫性能が発揮されないおそれがあり、一方５０質量％を超えると担体の割合が少なくなって、吸着剤の機械的強度や脱硫性能が低下する原因となる。該活性金属種のより好ましい含有量は、金属として３〜３０質量％の範囲である。
一方、当該吸着剤における担体としては、周期表第３族に属する金属元素の酸化物単独からなるものであってもよく、耐火性多孔質担体に、周期表第３族に属する金属元素の酸化物を含有させたものであってもよいが、当該吸着剤中の上記周期表第３族に属する金属元素の酸化物の含有量は、５〜９９質量％の範囲が好ましい。この含有量が上記範囲を逸脱すると十分な脱硫性能が発揮されない場合がある。周期表第３族に属する金属元素の酸化物のより好ましい含有量は１０〜９７質量％の範囲である。
【０００８】
前記周期表第３族に属する金属元素の酸化物としては、例えばＬａ、Ｃｅ、Ｓｃ、Ｙ、Ｎｄ、Ｐｒ、Ｓｍ、Ｇｄ及びＹｂの中から選ばれる金属の酸化物を好ましく挙げることができる。これらの金属の酸化物は、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよいが、これらの中で、Ｌａ、Ｃｅ、Ｙ、Ｙｂの酸化物がより好ましく、特にＬａ、Ｃｅの酸化物が好適である。
当該吸着剤において、担体として、耐火性多孔質担体に前記周期表第３族に属する金属元素の酸化物を含有させたものを用いる場合には、該耐火性多孔質担体としては、例えばシリカ、アルミナ、シリカ−アルミナ、チタニア、ジルコニア、ゼオライト、マグネシア、珪藻土、白土及び粘土などの中から選ばれる少なくとも一種を用いることができる。
本発明において、周期表第３族に属する金属元素の酸化物単独からなる担体を調製するには、例えば周期表第３族に属する金属元素源、具体的には該金属元素の硝酸塩などを含む水溶液とアルカリ水溶液とを接触させて沈殿を生成させ、次いで該沈殿をろ取、水洗し、５０〜２００℃程度の温度で乾燥したのち、２５０〜５００℃程度の温度で焼成処理すればよい。
【０００９】
また、耐火性多孔質担体に、周期表第３族に属する金属元素の酸化物を含有させるには、従来公知の方法、例えばポアフィリング法、浸漬法、蒸発乾固法などを用いることができる。この際、乾燥温度は、通常５０〜２００℃程度であり、焼成温度は、通常２５０〜５００℃程度である。
このようにして調製された担体に、銀や銅の活性金属種を担持させる方法としては、上記と同様に従来公知の方法、例えばポアフィリング法、浸漬法、蒸発乾固法などを採用することができる。この際、乾燥温度は、通常５０〜２００℃程度であり、また焼成温度は、通常２５０〜５００℃程度である。
このようにして得られた本発明の吸着剤は、ＬＰＧ、都市ガス、天然ガス、又はエタン、エチレン、プロパン、プロピレン及びブタンの中から選ばれる少なくとも一種を含むガスなどの炭化水素含有ガス中の硫黄化合物に対し、優れた脱硫性能を示す。例えばメルカプタン類、サルファイド類、ＣＯＳなど、ガス中に含まれるあらゆる硫黄化合物に対し、常温でも優れた吸着性能を示す。
【００１０】
本発明の吸着剤が適用される炭化水素含有ガス中の硫黄化合物の濃度としては、０．００１〜１０，０００容量ｐｐｍが好ましく、特に０．１〜１００容量ｐｐｍが好ましい。また、脱硫条件としては、通常温度は−５０〜３５０℃の範囲で選ばれ、ＧＨＳＶ（ガス時空間速度）は１００〜１，０００，０００ｈ−１の範囲で選ばれる。
次に、本発明の燃料電池用水素の製造方法においては、前述の本発明の吸着剤を用いて、炭化水素含有ガス中の硫黄化合物を脱硫処理したのち、脱硫処理炭化水素含有ガスを部分酸化触媒、オートサーマル改質触媒又は水蒸気改質触媒と接触させることにより、水素を製造する。
この方法においては、脱硫処理炭化水素含有ガス中の硫黄化合物の濃度は、各改質触媒の寿命の点から、０．２容量ｐｐｍ以下が好ましく、特に０．０５容量ｐｐｍ以下が好ましい。
また、部分酸化触媒、オートサーマル改質触媒および水蒸気改質触媒としては、ニッケル系又はルテニウム系触媒が好適である。また、部分酸化法、オートサーマル改質法及び水蒸気改質法としては、特に制限はなく従来公知の方法を適用することができる。
【００１１】
【実施例】
次に、本発明を実施例により、さらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
実施例１
硝酸セリウム３０質量％水溶液を、約５０℃に保持した１モル／リットル濃度の水酸化ナトリウム水溶液に攪拌しながら滴下し、沈殿を生成させた。次いで、生成した沈殿をろ取し、十分に水洗したのち、１２０℃で乾燥後、４００℃で焼成処理し、酸化セリウムを得た。
次に、この酸化セリウムに４２質量％濃度の硝酸銀水溶液を含浸させ、乾燥したのち、４００℃で焼成処理することにより、吸着剤を得た。この吸着剤中のＡｇの含有量は１０質量％であった。
【００１２】
実施例２
実施例１において、硝酸銀水溶液の代わりに硝酸銅水溶液を用いた以外は、実施例１と同様に吸着剤を調製した。この吸着剤中のＣｕの含有量は１０質量％であった。
実施例３
実施例１において、Ａｇの含有量を２０質量％とした以外は、実施例１と同様にして吸着剤を調製した。
実施例４
実施例１において、Ａｇの含有量を５質量％とした以外は、実施例１と同様にして吸着剤を調製した。
【００１３】
実施例５
実施例１において、硝酸セリウム水溶液の代わりに硝酸ランタン水溶液を用いた以外は、実施例１と同様にして吸着剤を調製した。この吸着剤中のＡｇの含有量は１０質量％であった。
実施例６
実施例１において、硝酸セリウム水溶液の代わりに硝酸イッテルビウム水溶液を用いた以外は、実施例１と同様にして吸着剤を調製した。この吸着剤中のＡｇの含有量は１０質量％であった。
実施例７
実施例１において、硝酸セリウム水溶液の代わりに硝酸イットリウム水溶液を用いた以外は、実施例１と同様にして吸着剤を調製した。この吸着剤中のＡｇの含有量は１０質量％であった。
【００１４】
実施例８
アルミナに硝酸セリウム５１質量％水溶液を含浸させ、乾燥後、４００℃で焼成処理し、ＣｅＯ２として２０質量％を含有する担体を得た。次いで、この担体に１９質量％濃度の硝酸銀水溶液を含浸させ、乾燥したのち、４００℃で焼成処理することにより、吸着剤を得た。この吸着剤中の酸化セリウムの含有量はＣｅＯ２として１８質量％、Ａｇの含有量は１０質量％であった。
比較例１
β型ゼオライト（東ソー社製、商品名「ＨＳＺ−９３０ＮＨＡ」）をＡｇイオンと交換したのち、５００℃で焼成することにより、Ａｇ交換β型ゼオライトからなる吸着剤を得た。この吸着剤中のＡｇの含有量は６．５質量％であった。
比較例２
市販のＣｕＺｎＡｌ触媒（ズードケミー社製、触媒「Ｇ−１３２Ｂ」）を吸着剤とした。
比較例３
市販のＡｇ／Ａｌ２Ｏ３触媒（ズードケミー社製、触媒「Ｔ−２５５２」）を吸着剤とした。
比較例４
実施例１で調製した酸化セリウム（Ａｇ未担持）を吸着剤とした。
【００１５】
試験例１
実施例１〜８及び比較例１〜４の各吸着剤を０．５〜１ｍｍに成型し、吸着剤１ｃｍ３を内径９ｍｍの脱硫管に充填した。常圧で吸着剤温度を２０℃とし、ＣＯＳ、ジメチルサルファイド（ＤＭＳ）、ｔ−ブチルメルカプタン（ＴＢＭ）及びジメチルジサルファイド（ＤＭＤＳ）を各１０ｖｏｌｐｐｍ（合計４０ｖｏｌｐｐｍ）含むプロパンガスを、常圧、ＧＨＳＶ（ガス時空間速度）３０，０００ｈ−１の条件で流通させた。
脱硫管出口ガスの各硫黄化合物濃度をＳＣＤ（化学発光硫黄検出器）ガスクロマトグラフィーにより、１時間毎に測定した。第１表に、各硫黄化合物濃度が０．１ｖｏｌｐｐｍを超える時間を示した。
【００１６】
【表１】
第１表から明らかなように、本発明の吸着剤（実施例１〜８）は、炭化水素含有ガス中の硫黄化合物を、常温において効率よく吸着除去し得ることが分かる。
【００１８】
【発明の効果】
本発明によれば、炭化水素含有ガス中の硫黄分を、室温においても低濃度まで効率よく除去し得る硫黄化合物除去用吸着剤、及び上記吸着剤を用いて脱硫処理した炭化水素含有ガスから、燃料電池用水素を効果的に製造する方法を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an adsorbent for removing sulfur compounds and a method for producing hydrogen for a fuel cell, and more particularly, to an adsorbent for removing sulfur compounds that can efficiently remove a sulfur content in a hydrocarbon-containing gas to a low concentration even at room temperature. The present invention relates to a method for effectively producing hydrogen for fuel cells from a hydrocarbon-containing gas desulfurized using the adsorbent and the adsorbent.
[0002]
[Prior art]
When producing hydrogen for fuel cells by reforming LPG or city gas, it is necessary to reduce the sulfur content in the gas to 0.01 ppm or less in order to suppress poisoning of the reforming catalyst. . In addition, when propylene, butene, or the like is used as a raw material for petrochemical products, it is required to reduce the sulfur content to 0.01 ppm or less in order to prevent poisoning of the catalyst.
In the LPG, dimethyl sulfide (DMS), t-butyl mercaptan (TBM), methyl ethyl sulfide and the like added as an odorant are generally added as sulfur compounds in addition to methyl mercaptan and carbonyl sulfide (COS). include. Various adsorbents for adsorbing and removing sulfur in fuel gas such as LPG are known. However, although some of these adsorbents show high desulfurization performance at about 150 to 300 ° C., the actual situation is that the desulfurization performance at room temperature is not always sufficiently satisfactory.
[0003]
For example, a desulfurizing agent in which Ag, Cu, Zn, Fe, Co, Ni, or the like is supported on a hydrophobic zeolite by ion exchange (for example, see Patent Document 1), or Ag or Y on a zeolite, a β zeolite, or an X zeolite A desulfurizing agent supporting Cu (for example, see Patent Document 2) is disclosed. However, it has been found that these desulfurizing agents can efficiently adsorb and remove mercaptans and sulfides at room temperature, but hardly adsorb carbonyl sulfide.
Further, a copper-zinc-based desulfurizing agent is disclosed (for example, see Patent Document 3). However, this desulfurizing agent can adsorb and remove various sulfur compounds including COS at a temperature of 150 ° C. or higher, but has low adsorption performance for sulfur compounds at a low temperature of 100 ° C. or lower. Furthermore, a desulfurizing agent in which copper is supported on a porous carrier such as alumina is disclosed (for example, see Patent Document 4). Although it is stated that this desulfurizing agent can be used at a temperature of 100 ° C. or less, its adsorption performance is not sufficiently satisfactory.
[0004]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 2001-286753 [Patent Document 2]
JP 2001-305123 A [Patent Document 3]
JP-A-2-302496 (page 2)
[Patent Document 4]
JP 2001-123188 A (page 3)
[0005]
[Problems to be solved by the invention]
Under such circumstances, the present invention provides a sulfur compound removing adsorbent capable of efficiently removing a sulfur content in a hydrocarbon-containing gas to a low concentration even at room temperature, and a carbon desulfurized using the adsorbent. It is an object of the present invention to provide a method for effectively producing hydrogen for a fuel cell from a hydrogen-containing gas.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to achieve the above object, and as a result, a carrier containing a specific metal oxide and a certain metal or its oxide supported on a carrier containing a specific metal oxide are adsorbents for removing sulfur compounds. The present inventors have found that hydrogen for fuel cells can be effectively obtained by reforming a hydrocarbon-containing gas desulfurized using this adsorbent. The present invention has been completed based on such findings.
That is, the present invention
(1) A carrier containing an oxide of a metal element belonging to Group 3 of the periodic table, on a carrier containing at least one selected from silver and its oxides and copper and its oxides. Adsorbent for removing sulfur compounds,
(2) The oxide of a metal element belonging to Group 3 of the periodic table is an oxide of at least one metal selected from La, Ce, Sc, Y, Nd, Pr, Sm, Gd, and Yb. 1) an adsorbent for removing sulfur compounds in a hydrocarbon-containing gas,
(3) The sulfur in the hydrocarbon-containing gas of (2) above, wherein the oxide of the metal element belonging to Group 3 of the periodic table is an oxide of at least one metal selected from La, Yb, Y and Ce. Adsorbent for compound removal,
(4) The hydrocarbon according to the above (1) to (3), wherein the hydrocarbon-containing gas is LPG, city gas, natural gas, or a gas containing at least one selected from ethane, ethylene, propane, propylene and butane. Adsorbent for removing sulfur compounds in the contained gas,
(5) The metal of the above (1) to (4), wherein the amount of at least one selected from silver and its oxides and copper and its oxides is 1 to 50% by mass as a metal based on the total amount of the adsorbent. Adsorbent for removing sulfur compounds in hydrocarbon-containing gas,
(6) The hydrocarbon-containing gas according to claim 5, wherein the carried amount of at least one selected from silver and its oxides and copper and its oxides is 3 to 30% by mass as the metal based on the total amount of the adsorbent. Adsorbent for removing sulfur compounds in
(7) The adsorbent for removing a sulfur compound in a hydrocarbon-containing gas according to (1) to (6), wherein the content of the oxide of the metal element belonging to Group 3 of the periodic table is 5 to 99% by mass;
(8) After the sulfur compounds in the hydrocarbon-containing gas are desulfurized using the adsorbents of the above (1) to (7), the desulfurized hydrocarbon-containing gas is subjected to a partial oxidation catalyst, an autothermal reforming catalyst, or steam. (9) The method for producing hydrogen for a fuel cell, which is brought into contact with a reforming catalyst, and (9) the above (8), wherein the partial oxidation catalyst, the autothermal reforming catalyst or the steam reforming catalyst is a ruthenium-based or nickel-based catalyst. Method for producing hydrogen for fuel cells,
Is provided.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
The sulfur compound adsorbent of the present invention is obtained by supporting an active metal species on a support containing an oxide of a metal element belonging to Group 3 of the periodic table. As the active metal species, silver and its oxide and At least one selected from copper and its oxides is used.
In the adsorbent, the content of the active metal species is preferably in a range of 1 to 50% by mass as a metal (silver and / or copper). When the content of the active metal species is less than 1% by mass, sufficient desulfurization performance may not be exhibited. On the other hand, when the content exceeds 50% by mass, the ratio of the carrier decreases, and the mechanical strength and desulfurization performance of the adsorbent decrease. Cause you to A more preferred content of the active metal species is in the range of 3 to 30% by mass as a metal.
On the other hand, the carrier in the adsorbent may be composed of an oxide of a metal element belonging to Group 3 of the periodic table alone. However, the content of the oxide of the metal element belonging to Group 3 of the periodic table in the adsorbent is preferably in the range of 5 to 99% by mass. If this content is outside the above range, sufficient desulfurization performance may not be exhibited. The more preferable content of the oxide of the metal element belonging to Group 3 of the periodic table is in the range of 10 to 97% by mass.
[0008]
As the oxide of the metal element belonging to Group 3 of the periodic table, for example, an oxide of a metal selected from La, Ce, Sc, Y, Nd, Pr, Sm, Gd and Yb can be preferably exemplified. These metal oxides may be used alone or in combination of two or more. Among them, La, Ce, Y, and Yb oxides are more preferable, and in particular, La is preferable. , Ce oxides are preferred.
In the adsorbent, when using a refractory porous carrier containing an oxide of a metal element belonging to Group 3 of the periodic table as the carrier, the refractory porous carrier may be, for example, silica, At least one selected from alumina, silica-alumina, titania, zirconia, zeolite, magnesia, diatomaceous earth, clay, clay and the like can be used.
In the present invention, in order to prepare a carrier composed of an oxide of a metal element belonging to Group 3 of the periodic table alone, for example, a source of a metal element belonging to Group 3 of the periodic table, specifically, a nitrate of the metal element, and the like are included. An aqueous solution and an alkaline aqueous solution are brought into contact with each other to form a precipitate, and then the precipitate is collected by filtration, washed with water, dried at a temperature of about 50 to 200 ° C, and then calcined at a temperature of about 250 to 500 ° C.
[0009]
In addition, in order to make the refractory porous carrier contain an oxide of a metal element belonging to Group 3 of the periodic table, a conventionally known method such as a pore filling method, an immersion method, and an evaporation to dryness method can be used. . At this time, the drying temperature is usually about 50 to 200 ° C, and the firing temperature is usually about 250 to 500 ° C.
As a method for supporting the active metal species of silver or copper on the carrier prepared in this manner, a conventionally known method, such as a pore filling method, an immersion method, an evaporation to dryness method, or the like may be employed as described above. Can be. At this time, the drying temperature is usually about 50 to 200 ° C, and the firing temperature is usually about 250 to 500 ° C.
The adsorbent of the present invention obtained in this manner can be used in a hydrocarbon-containing gas such as LPG, city gas, natural gas, or a gas containing at least one selected from ethane, ethylene, propane, propylene and butane. Shows excellent desulfurization performance for sulfur compounds. For example, it exhibits excellent adsorption performance at room temperature to all sulfur compounds contained in gas, such as mercaptans, sulfides, and COS.
[0010]
The concentration of the sulfur compound in the hydrocarbon-containing gas to which the adsorbent of the present invention is applied is preferably 0.001 to 10,000 ppm by volume, particularly preferably 0.1 to 100 ppm by volume. As the desulfurization conditions, the temperature is usually selected in the range of -50 to 350C, and the GHSV (gas hourly space velocity) is selected in the range of 100 to 1,000,000 h- 1 .
Next, in the method for producing hydrogen for a fuel cell of the present invention, after the sulfur compound in the hydrocarbon-containing gas is desulfurized using the adsorbent of the present invention, the desulfurized hydrocarbon-containing gas is partially oxidized. Hydrogen is produced by contact with a catalyst, an autothermal reforming catalyst or a steam reforming catalyst.
In this method, the concentration of the sulfur compound in the desulfurized hydrocarbon-containing gas is preferably 0.2 ppm by volume or less, particularly preferably 0.05 ppm by volume or less, from the viewpoint of the life of each reforming catalyst.
As the partial oxidation catalyst, the autothermal reforming catalyst and the steam reforming catalyst, nickel-based or ruthenium-based catalysts are suitable. The partial oxidation method, the autothermal reforming method and the steam reforming method are not particularly limited, and conventionally known methods can be applied.
[0011]
【Example】
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1
A 30% by mass aqueous cerium nitrate solution was added dropwise to a 1 mol / liter aqueous sodium hydroxide solution kept at about 50 ° C. while stirring to form a precipitate. Next, the generated precipitate was collected by filtration, sufficiently washed with water, dried at 120 ° C., and calcined at 400 ° C. to obtain cerium oxide.
Next, the cerium oxide was impregnated with an aqueous solution of silver nitrate having a concentration of 42% by mass, dried, and calcined at 400 ° C. to obtain an adsorbent. The content of Ag in this adsorbent was 10% by mass.
[0012]
Example 2
An adsorbent was prepared in the same manner as in Example 1, except that an aqueous copper nitrate solution was used instead of the aqueous silver nitrate solution. The content of Cu in this adsorbent was 10% by mass.
Example 3
An adsorbent was prepared in the same manner as in Example 1, except that the Ag content was changed to 20% by mass.
Example 4
An adsorbent was prepared in the same manner as in Example 1, except that the Ag content was changed to 5% by mass.
[0013]
Example 5
An adsorbent was prepared in the same manner as in Example 1 except that a lanthanum nitrate aqueous solution was used instead of the cerium nitrate aqueous solution. The content of Ag in this adsorbent was 10% by mass.
Example 6
An adsorbent was prepared in the same manner as in Example 1, except that an aqueous ytterbium nitrate solution was used instead of the aqueous cerium nitrate solution. The content of Ag in this adsorbent was 10% by mass.
Example 7
An adsorbent was prepared in the same manner as in Example 1 except that an aqueous solution of yttrium nitrate was used instead of the aqueous solution of cerium nitrate. The content of Ag in this adsorbent was 10% by mass.
[0014]
Example 8
Alumina was impregnated with a 51% by mass aqueous solution of cerium nitrate, dried, and calcined at 400 ° C. to obtain a carrier containing 20% by mass as CeO 2 . Next, the carrier was impregnated with a 19% by mass aqueous solution of silver nitrate, dried, and calcined at 400 ° C. to obtain an adsorbent. The content of cerium oxide in this adsorbent was 18% by mass as CeO 2 , and the content of Ag was 10% by mass.
Comparative Example 1
After exchanging the β-type zeolite (trade name “HSZ-930NHA” manufactured by Tosoh Corporation) with Ag ions, it was calcined at 500 ° C. to obtain an adsorbent composed of the Ag-exchanged β-type zeolite. The Ag content in this adsorbent was 6.5% by mass.
Comparative Example 2
A commercially available CuZnAl catalyst (manufactured by Sudo Chemie, catalyst "G-132B") was used as the adsorbent.
Comparative Example 3
A commercially available Ag / Al 2 O 3 catalyst (catalyst “T-2552” manufactured by Sudochemie) was used as the adsorbent.
Comparative Example 4
Cerium oxide (not carrying Ag) prepared in Example 1 was used as an adsorbent.
[0015]
Test example 1
Each of the adsorbents of Examples 1 to 8 and Comparative Examples 1 to 4 was molded to a size of 0.5 to 1 mm, and 1 cm 3 of the adsorbent was filled in a desulfurization tube having an inner diameter of 9 mm. At normal pressure, the adsorbent temperature is set to 20 ° C., and propane gas containing 10 vol ppm (40 vol ppm in total) of COS, dimethyl sulfide (DMS), t-butyl mercaptan (TBM), and dimethyl disulfide (DMDS) at normal pressure and GHSV ( It was circulated under the condition of (gas hourly space velocity) 30,000 h −1 .
The concentration of each sulfur compound in the gas at the outlet of the desulfurization tube was measured every hour by SCD (chemiluminescence sulfur detector) gas chromatography. Table 1 shows the time when the concentration of each sulfur compound exceeded 0.1 volppm.
[0016]
[Table 1]
As is clear from Table 1, it can be seen that the adsorbent of the present invention (Examples 1 to 8) can efficiently adsorb and remove sulfur compounds in a hydrocarbon-containing gas at ordinary temperature.
[0018]
【The invention's effect】
According to the present invention, a sulfur component in a hydrocarbon-containing gas, a sulfur compound removal adsorbent capable of efficiently removing even a low concentration even at room temperature, and a hydrocarbon-containing gas desulfurized using the adsorbent, A method for effectively producing hydrogen for a fuel cell can be provided.
Claims (9)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002259768A JP4216548B2 (en) | 2002-09-05 | 2002-09-05 | Adsorbent for removing sulfur compounds and method for producing hydrogen for fuel cell |
| CA2497899A CA2497899C (en) | 2002-09-05 | 2003-08-26 | Adsorbent for removing sulfur compound, process for producing hydrogen and fuel cell system |
| EP03794097A EP1550505A4 (en) | 2002-09-05 | 2003-08-26 | Adsorbent for removing sulfur compound, process for producing hydrogen and fuel cell system |
| PCT/JP2003/010781 WO2004022224A1 (en) | 2002-09-05 | 2003-08-26 | Adsorbent for removing sulfur compound, process for producing hydrogen and fuel cell system |
| AU2003261728A AU2003261728A1 (en) | 2002-09-05 | 2003-08-26 | Adsorbent for removing sulfur compound, process for producing hydrogen and fuel cell system |
| CNB038210339A CN100469434C (en) | 2002-09-05 | 2003-08-26 | Adsorbent for removing sulfur compounds, method for producing hydrogen, and fuel cell system |
| KR1020057003716A KR100973876B1 (en) | 2002-09-05 | 2003-08-26 | Adsorbent for removing sulfur compound, process for producing hydrogen and fuel cell system |
| US10/526,397 US7556872B2 (en) | 2002-09-05 | 2003-08-26 | Adsorbent for removing sulfur compound, process for producing hydrogen and fuel cell system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002259768A JP4216548B2 (en) | 2002-09-05 | 2002-09-05 | Adsorbent for removing sulfur compounds and method for producing hydrogen for fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004097870A true JP2004097870A (en) | 2004-04-02 |
| JP4216548B2 JP4216548B2 (en) | 2009-01-28 |
Family
ID=32260667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002259768A Expired - Fee Related JP4216548B2 (en) | 2002-09-05 | 2002-09-05 | Adsorbent for removing sulfur compounds and method for producing hydrogen for fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4216548B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006044965A (en) * | 2004-08-02 | 2006-02-16 | Idemitsu Kosan Co Ltd | Method for manufacturing zeolite and adsorbent containing the zeolite for removing sulfur compound |
-
2002
- 2002-09-05 JP JP2002259768A patent/JP4216548B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006044965A (en) * | 2004-08-02 | 2006-02-16 | Idemitsu Kosan Co Ltd | Method for manufacturing zeolite and adsorbent containing the zeolite for removing sulfur compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4216548B2 (en) | 2009-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5220265B2 (en) | Method for removing sulfur compounds from hydrocarbon-containing gas | |
| DK2438145T3 (en) | METHOD OF SULFURING A FUEL FLOW | |
| US8308848B1 (en) | High temperature gas desulfurization sorbents | |
| US20060283780A1 (en) | Desulfurization system and method for desulfurizing a fuel stream | |
| KR100973876B1 (en) | Adsorbent for removing sulfur compound, process for producing hydrogen and fuel cell system | |
| KR20070019428A (en) | Desulfurizing agent for removing organic sulfides, method of preparing thereof and method for removing organic sulfur compounds using the same | |
| JP4722429B2 (en) | Method for producing metal-supported zeolite molding and adsorbent for removing sulfur compound containing the zeolite | |
| JP4452097B2 (en) | Method for producing cerium oxide molded body | |
| JP2006501065A (en) | Catalyst adsorbent for sulfur compound removal for fuel cells | |
| JP3742284B2 (en) | Adsorbent for sulfur compounds in fuel gas and method for removing the same | |
| JP3483827B2 (en) | Lifetime determination method for sulfur compound adsorbent in fuel gas | |
| JP2004168648A (en) | Metal ion-exchange zeolite, its manufacturing method, and adsorbent containing the metal ion-exchange zeolite for removing sulfur compound | |
| JP4079743B2 (en) | Desulfurizing agent for hydrocarbon-containing gas and method for producing hydrogen for fuel cell | |
| JP2018108927A (en) | Metal-supported zeolite molded body, production method of metal-supported zeolite molded body, absorbent for removing sulfur compound, production method of hydrogen, and fuel cell system | |
| JP4216548B2 (en) | Adsorbent for removing sulfur compounds and method for producing hydrogen for fuel cell | |
| JP6317909B2 (en) | Metal-supported zeolite molded body, metal-supported zeolite molded body manufacturing method, sulfur compound removing adsorbent, hydrogen manufacturing method, and fuel cell system | |
| JP2005007383A (en) | Adsorbent for removing sulfur compound and method for producing hydrogen for fuel cell | |
| JP2004305869A (en) | Adsorbent for removing sulfur compound, and method for producing hydrogen for fuel cell | |
| JP3926170B2 (en) | Method for removing sulfur compounds | |
| JP4779620B2 (en) | How to use room temperature NOx adsorbent | |
| JP4961102B2 (en) | Method for producing zeolite and adsorbent for removing sulfur compound containing the zeolite | |
| JP4722454B2 (en) | Method for producing adsorbent for removing sulfur compound, adsorbent for removing sulfur compound, and method for removing sulfur compound | |
| JPH02302496A (en) | Desulfurizing method of town gas | |
| JP2013199533A (en) | Method for producing desulfurized gaseous fuel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050616 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080729 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080929 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20081028 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20081106 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111114 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141114 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |