JP7347541B2 - 炭化水素改質触媒、炭化水素改質装置、および、炭化水素改質触媒の硫黄劣化回復方法 - Google Patents
炭化水素改質触媒、炭化水素改質装置、および、炭化水素改質触媒の硫黄劣化回復方法 Download PDFInfo
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- JP7347541B2 JP7347541B2 JP2021569737A JP2021569737A JP7347541B2 JP 7347541 B2 JP7347541 B2 JP 7347541B2 JP 2021569737 A JP2021569737 A JP 2021569737A JP 2021569737 A JP2021569737 A JP 2021569737A JP 7347541 B2 JP7347541 B2 JP 7347541B2
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
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Description
ペロブスカイト構造を有する複合酸化物を含み、
前記複合酸化物は、CaZrO3を主成分とする結晶相を有し、かつ、Ruと、CeおよびYのうちの少なくとも一方とを含むことを特徴とする。
C3H8+3H2O → 7H2+3CO (1)
C3H8+3CO2 → 4H2+6CO (2)
炭化水素改質触媒の材料として、CaCO3、ZrO2、CeO2、Y2O3、および、RuO2を用意し、Ca:Zr:Ce:Y:Ruのモル比が表1に示す割合となるように秤量し、玉石と水とバインダーを加えて湿式混合し、混合物を得た。得られた混合物をオーブン内で120℃の温度で乾燥させた後、粉砕、分級することによって、約2mmの大きさの粒状とした。その後、粒状試料を空気中で1000℃、1時間の条件で焼成することにより、実施例1~8の炭化水素改質触媒を得た。
炭化水素改質触媒の材料として、CaCO3、ZrO2、CeO2、および、RuO2を用意し、Ca:Zr:Ce:Ruのモル比が表1に示す割合となるように秤量し、玉石と水とバインダーを加えて湿式混合し、混合物を得た。この後、実施例1~8の炭化水素改質触媒を作製する方法と同じ方法によって、実施例9~11の炭化水素改質触媒を作製した。
炭化水素改質触媒の材料として、CaCO3、ZrO2、Y2O3、および、RuO2を用意し、Ca:Zr:Y:Ruのモル比が表1に示す割合となるように秤量し、玉石と水とバインダーを加えて湿式混合し、混合物を得た。この後、実施例1~8の炭化水素改質触媒を作製する方法と同じ方法によって、実施例12~14の炭化水素改質触媒を作製した。
炭化水素改質触媒の材料として、CaCO3、ZrO2、および、RuO2を用意し、Ca:Zr:Ruのモル比が表1に示す割合となるように秤量し、玉石と水とバインダーを加えて湿式混合し、混合物を得た。この後、実施例1~8の炭化水素改質触媒を作製する方法と同じ方法によって、参考例1の炭化水素改質触媒を作製した。
炭化水素改質触媒の材料として、CaCO3、CeO2、および、RuO2を用意し、Ca:Ce:Ruのモル比が表1に示す割合となるように秤量し、玉石と水とバインダーを加えて湿式混合し、混合物を得た。この後、実施例1~8の炭化水素改質触媒を作製する方法と同じ方法によって、比較例1の炭化水素改質触媒を作製した。
炭化水素改質触媒の材料として、CaCO3、ZrO2、および、RuO2を用意し、Ca:Zr:Ruのモル比が表1に示す割合となるように秤量し、玉石と水とバインダーを加えて湿式混合し、混合物を得た。この混合物におけるCa:Zr:Ruのモル比は、参考例1の炭化水素改質触媒を作製する際に用いた材料のCa:Zr:Ruのモル比と同じである。この後、焼成温度を600℃とした以外は、参考例1の炭化水素改質触媒を作製する方法と同じ方法によって、比較例2の炭化水素改質触媒を作製した。比較例2の炭化水素改質触媒は、本発明の要件を満たしていない触媒である。
炭化水素改質触媒の材料として、CaCO3、ZrO2、CeO2、Y2O3、および、RuO2を用意し、Ca:Zr:Ce:Y:Ruのモル比が表1に示す割合となるように秤量し、玉石と水とバインダーを加えて湿式混合し、混合物を得た。この混合物におけるCa:Zr:Ce:Y:Ruのモル比は、実施例5の炭化水素改質触媒を作製する際に用いた材料のCa:Zr:Ce:Y:Ruのモル比と同じである。この後、焼成温度を600℃とした以外は、実施例5の炭化水素改質触媒を作製する方法と同じ方法によって、比較例3の炭化水素改質触媒を作製した。比較例3の炭化水素改質触媒は、本発明の要件を満たしていない触媒である。
上述した実施例1~14、参考例1および比較例1~3の炭化水素改質触媒を乳鉢で粉砕し、粉末XRD測定によって、結晶相を確認した。粉末XRD測定では、X線としてCu-Kα1を用いた。
実施例1~14および参考例1の炭化水素改質触媒と、比較例1~3の炭化水素改質触媒をそれぞれ乳鉢で細かく粉砕し、得られた粉末に対して蛍光X線分析(XRF分析)による組成分析を行った。その結果、組成分析を行った全ての炭化水素改質触媒について、秤量時の配分の元素モル比を維持しており、加熱焼成処理による各成分の減少などの元素モル比の変化がないことを確認した。
実施例1~14、参考例1および比較例1~3の炭化水素改質触媒それぞれ粉砕、分級して0.5mm~0.7mmの大きさにした後、以下の方法により、炭化水素系ガスであるプロパンガスの水蒸気改質評価試験を行った。ただし、炭化水素系ガスがプロパンガスに限定されることはない。
原料ガス導入から最初の1時間は硫黄成分が存在しない状態として、1時間後の水素濃度(初期の水素濃度)を測定し、炭化水素改質触媒の初期活性を確認した。表2に、各実施例、参考例および比較例の炭化水素改質触媒を用いた場合に、ガス排出管5から排出される水素の濃度(初期の水素濃度)と、初期活性の平衡到達率を示す。初期活性の平衡到達率は、次式(3)により定義した。
初期活性の平衡到達率=初期の水素濃度/平衡水素濃度×100 (3)
上記初期活性の確認後、原料ガスの合計流量477cc/分に対して50ppmの割合となるようにSO2ガスを混合し、1時間後の水素ガス濃度を測定して、硫黄存在下における触媒の活性劣化を確認したところ、実施例1~14、参考例1および比較例1~3の炭化水素改質触媒の全てにおいて、水素濃度は0か、または、かなり低い値となった。
上記硫黄劣化後の特性確認後、管1に、炭化水素系ガスを含まない混合ガス、具体的には、窒素(N2)を350cc/分、水蒸気(H2O)を60cc/分、二酸化炭素(CO2)を60cc/分の流量で導入しながら炭化水素改質触媒を800℃まで加熱し、800℃のまま1時間加熱処理を行った。その後、温度を600℃まで下げ、再び、窒素(N2)を350cc/分、プロパン(C3H8)を7cc/分、水蒸気(H2O)を60cc/分、二酸化炭素(CO2)を60cc/分の流量で導入して、1時間後の水素濃度を測定し、加熱処理後の炭化水素改質触媒の活性を確認した。
加熱処理後の平衡到達率=加熱処理後の水素濃度/平衡水素濃度×100 (4)
表2に示すように、本発明の要件を満たす実施例1~14の炭化水素改質触媒を用いた場合、初期活性の平衡到達率は52%以上となった。これに対して、本発明の要件を満たしていない比較例1~3の炭化水素改質触媒を用いた場合には、初期活性の平衡到達率は19%以下と低い値になった。
上述したように、原料ガスに硫黄成分が含まれる場合、触媒活性が低下する。しかしながら、表2に示すように、本発明の要件を満たす炭化水素改質触媒では、加熱処理後の平衡到達率が31%以上となった。すなわち、硫黄劣化により触媒活性が低下した場合でも、加熱処理することによって、触媒活性が回復することが分かる。したがって、硫黄が存在する環境下で本発明の要件を満たす炭化水素改質触媒が使用される場合でも、定期的に加熱処理を行うことで、継続的に使用することが可能となる。
2 加熱部
3 炭化水素改質触媒
4 ガス供給管
5 ガス排出管
6 炭化水素供給源
7 水素取り出し口
100 炭化水素改質装置
Claims (7)
- 炭化水素系ガスから水素と一酸化炭素とを含む合成ガスを生成する際に用いられる触媒であって、
ペロブスカイト構造を有する複合酸化物を含み、
前記複合酸化物は、CaZrO3を主成分とする結晶相を有し、かつ、Ruと、CeおよびYのうちの少なくとも一方とを含み、
Caに対するRuのモル比は、0.01以上0.29以下であることを特徴とする炭化水素改質触媒。 - 前記複合酸化物は、YとCeを含むことを特徴とする請求項1に記載の炭化水素改質触媒。
- Caに対するRuのモル比は、0.03以上0.29以下であることを特徴とする請求項2に記載の炭化水素改質触媒。
- 前記複合酸化物は、Yを含むがCeを含まないことを特徴とする請求項1に記載の炭化水素改質触媒。
- 前記複合酸化物は、Ceを含むがYを含まないことを特徴とする請求項1に記載の炭化水素改質触媒。
- 少なくとも炭化水素を含む被処理ガスが流通する管と、
前記管の内部の、前記被処理ガスと接触する位置に配置される、請求項1~5のいずれかに記載の炭化水素改質触媒と、
を備えることを特徴とする炭化水素改質装置。 - 硫黄により活性が低下した炭化水素改質触媒の硫黄劣化回復方法であって、
炭化水素系ガスが存在しない状態で、請求項1~5のいずれかに記載の炭化水素改質触媒を700℃以上の温度で所定時間加熱することを特徴とする炭化水素改質触媒の硫黄劣化回復方法。
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JP2010029846A (ja) | 2008-07-04 | 2010-02-12 | Murata Mfg Co Ltd | 二酸化炭素改質用触媒、その製造方法、二酸化炭素改質用触媒の担体、改質器、および合成ガスの製造方法 |
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