JP2016059844A - 水素製造用触媒、その製造方法及び燃料電池システム - Google Patents
水素製造用触媒、その製造方法及び燃料電池システム Download PDFInfo
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- JP2016059844A JP2016059844A JP2014187897A JP2014187897A JP2016059844A JP 2016059844 A JP2016059844 A JP 2016059844A JP 2014187897 A JP2014187897 A JP 2014187897A JP 2014187897 A JP2014187897 A JP 2014187897A JP 2016059844 A JP2016059844 A JP 2016059844A
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- catalyst
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- hydrogen production
- reforming
- hydrogen
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Images
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
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- Fuel Cell (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
Description
La1−xSrxAlO3 (但し、0≦x≦0.5) (I)
La1−xSrxAlO3 (但し、0≦x≦0.5) (I)
La(NO3)3・6H2O 7.63g、Sr(NO3)2 1.60g、Al(NO3)3・9H2O 9.45g、クエン酸 31.76g、エチレングリコール 9.38g及び純水 200gを混合してよく撹拌した後、加熱して水分を除去した。次に、400℃で2時間保持して硝酸塩を分解させた後、800℃で10時間保持してクエン酸、エチレングリコールを燃焼除去することにより、La0.7Sr0.3AlO3で表される触媒担体A(LSAO)を得た。
La(NO3)3・6H2O 10.91g、Al(NO3)3・9H2O 0.45g、クエン酸 31.76g、エチレングリコール 9.38g及び純水 200gを混合してよく撹拌した後、加熱して水分を除去した。次に、400℃で2時間保持して硝酸塩を分解させた後、800℃で10時間保持してクエン酸、エチレングリコールを燃焼除去することにより、LaAlO3で表される触媒担体B(LAO)を得た。
[Ba/Ni/LSAOの調製]
上記触媒担体Aに、触媒の全量に対するNi含有量が5質量%となるようにNi(NO3)2水溶液を含浸させ、水分を蒸発させた。次に、120℃にて10時間乾燥させ、空気流通下800℃にて1時間焼成した。ついでNiが担持された担体に、触媒の全量に対するBa含有量が2.4質量%となるようにBa(NO3)2水溶液を含浸させて水分を蒸発させた。次に、120℃にて3時間乾燥させ、空気流通下800℃にて1時間焼成した。焼成した触媒を、加圧成形した後、粉砕してふるい分けし、平均粒径が約1〜2mmの顆粒状の触媒A1(Ba/Ni/LSAO)を得た。
[Ca/Ni/LSAOの調製]
上記触媒担体Aに、触媒の全量に対するNi含有量が5質量%となるようにNi(NO3)2水溶液を含浸させ、水分を蒸発させた。次に、120℃にて10時間乾燥させ、空気流通下800℃にて1時間焼成した。ついでNiが担持された担体に、触媒の全量に対するCa含有量が0.7質量%となるようにCa(NO3)2水溶液を含浸させて水分を蒸発させた。次に、120℃にて3時間乾燥させ、空気流通下800℃にて1時間焼成した。焼成した触媒を、加圧成形した後、粉砕してふるい分けし、平均粒径が約1〜2mmの顆粒状の触媒A2(Ca/Ni/LSAO)を得た。
[Sr/Ni/LSAOの調製]
上記触媒担体Aに、触媒の全量に対するNi含有量が5質量%となるようにNi(NO3)2水溶液を含浸させ、水分を蒸発させた。次に、120℃にて10時間乾燥させ、空気流通下800℃にて1時間焼成した。ついでNiが担持された担体に、触媒の全量に対するSr含有量が1.5質量%となるようにSr(NO3)2水溶液を含浸させて水分を蒸発させた。次に、120℃にて3時間乾燥させ、空気流通下800℃にて1時間焼成した。焼成した触媒を、加圧成形した後、粉砕してふるい分けし、平均粒径が約1〜2mmの顆粒状の触媒A3(Sr/Ni/LSAO)を得た。
[Ni/Ba/LAOの調製]
上記触媒担体Bに、触媒の全量に対するBa含有量が2.4質量%となるようにBa(NO3)2水溶液を含浸させ、水分を蒸発させた。次に、120℃にて3時間乾燥させ、空気流通下800℃にて1時間焼成した。ついでBaが担持された担体に、触媒の全量に対するNi含有量が5質量%となるようにNi(NO3)2水溶液を含浸させて水分を蒸発させた。次に、120℃にて3時間乾燥させ、空気流通下800℃にて1時間焼成した。焼成した触媒を、加圧成形した後、粉砕してふるい分けし、平均粒径が約1〜2mmの顆粒状の触媒B1(Ni/Ba/LAO)を得た。
[Ni/LSAOの調製]
上記触媒担体Aに、触媒の全量に対するNi含有量が5質量%となるようにNi(NO3)2水溶液を含浸させ、水分を蒸発させた。次に、120℃にて3時間乾燥させ、空気流通下800℃にて1時間焼成した。次いで、加圧成形した後、粉砕してふるい分けし、平均粒径が約1〜2mmの顆粒状の触媒A4(Ni/LSAO)を得た。
[Ni/LAOの調製]
上記触媒担体Bに、触媒の全量に対するNi含有量が5質量%となるようにNi(NO3)2水溶液を含浸させ、水分を蒸発させた。次に、120℃にて3時間乾燥させ、空気流通下800℃にて1時間焼成した。次いで、加圧成形した後、粉砕してふるい分けし、平均粒径が約1〜2mmの顆粒状の触媒B2(Ni/LAO)を得た。
[触媒A4(Ni/LSAO)の還元処理]
上記触媒A4を、水素流通下800℃で1時間還元処理し、触媒A5を得た。
[触媒B2(Ni/LAO)の還元処理]
上記触媒B2を、水素流通下800℃で1時間還元処理し、触媒B3を得た。
実施例1で得られた触媒A1を用いて、以下の方法により水蒸気改質反応(スチームリフォーミング反応)を行い、触媒A1の水蒸気活性及び触媒寿命を評価した。
まず、原料のトルエンを脱硫処理した後、得られた脱硫処理後のトルエンと水とを十分に混合してから気化させて、改質原料とした。得られた改質原料を、触媒A1を充填した改質器へ導入し、以下の反応条件にて水蒸気改質反応を行った。
[反応条件]
触媒量W:25mg
W/F:3.4gh/mol(ここで、Wは触媒量(g)、Fは原料供給速度(mol/h)を示す。)
反応温度:600℃
スチーム/カーボン比(モル比):2.0
トルエン転化率=(生成ガス中のCO、CO2、CH4のカーボンモル数)/(トルエンのカーボンモル数)×100(%)
上記触媒担体A及びBを、XRD装置としてRigaku社製RINT2500(線源:CuKα,モノクロメーター使用、電圧50KV、電源200mA)を用いて、下記の条件で分析した。
測定方法:集中法(連続)
発散スリット:1/2deg
発散縦制限スリット:10mm
散乱スリット:1/2deg
発光スリット:0.15mm
オフセット角:0deg
スキャンスピード:2deg/min
サンプリング幅:0.02deg
2θ:5〜90deg
Claims (6)
- 下記組成式(I)で表される酸化物を含有する担体と、
ニッケルと、カルシウム、ストロンチウム及びバリウムからなる群より選ばれる少なくとも一種以上の周期表第2族元素と、を含有する、水素製造用触媒。
La1−xSrxAlO3 (但し、0≦x≦0.5) (I) - 前記酸化物が、該酸化物の粉末X線回折スペクトルにおいて、2θが33°以上34°以下の範囲に最大の回折ピークを示すものである、請求項1に記載の水素製造用触媒。
- 前記ニッケルのモル数nNiに対する前記周期表第2族元素の合計モル数nMの比nM/nNiが、0.01以上20以下である、請求項1又は2に記載の水素製造用触媒。
- 請求項1〜3のいずれか一項に記載の水素製造用触媒を製造する方法であって、
下記組成式(I)で表される酸化物を含有する担体にニッケルを担持する第一の担持工程と、
前記ニッケルが担持された前記担体に周期表第2族元素を担持する第二の担持工程と、
を備える、水素製造用触媒の製造方法。
La1−xSrxAlO3 (但し、0≦x≦0.5) (I) - 前記第二の担持工程が、前記ニッケルが担持された前記担体に、周期表第2族元素が含まれる化合物を含浸したものを、300〜700℃で焼成する工程である、請求項4に記載の水素製造用触媒の製造方法。
- 炭化水素化合物類が含まれる改質原料を水素が含まれる改質ガスに改質する改質部、を備える燃料電池システムであって、
前記改質部が、請求項1〜3のいずれか一項に記載の水素製造用触媒又は請求項4若しくは5に記載の方法によって得られる水素製造用触媒を含む、燃料電池システム。
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JP2011206725A (ja) * | 2010-03-30 | 2011-10-20 | Jx Nippon Oil & Energy Corp | 水蒸気改質用触媒、水素製造装置及び燃料電池システム |
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