JP7044206B2 - 炭化水素改質触媒および炭化水素改質装置 - Google Patents
炭化水素改質触媒および炭化水素改質装置 Download PDFInfo
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- 229930195733 hydrocarbon Natural products 0.000 title claims description 142
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 142
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 140
- 239000003054 catalyst Substances 0.000 title claims description 135
- 238000002407 reforming Methods 0.000 title claims description 109
- 239000007789 gas Substances 0.000 claims description 67
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 30
- 239000013078 crystal Substances 0.000 claims description 29
- 229910052707 ruthenium Inorganic materials 0.000 claims description 17
- 229910052684 Cerium Inorganic materials 0.000 claims description 15
- 229910052788 barium Inorganic materials 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- 229910052727 yttrium Inorganic materials 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 239000012071 phase Substances 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 22
- 229910052717 sulfur Inorganic materials 0.000 description 22
- 239000011593 sulfur Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- 230000006866 deterioration Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 230000000977 initiatory effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000012790 confirmation Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000264877 Hippospongia communis Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 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
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- -1 lanthanum aluminate Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Description
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、BaCeO3を主成分とする結晶相を有し、かつ、Ruを含み、
前記複合酸化物に含まれるBaに対するRuのモル比は、0.04以上0.43以下であることを特徴とする。
C3H8+3H2O → 7H2+3CO (1)
C3H8+3CO2 → 4H2+6CO (2)
炭化水素改質触媒の材料として、BaCO3、ZrO2、CeO2、Y2O3、および、RuO2を用意し、Ba: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、0.5mm以上0.7mm以下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1~24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、BaCO3、ZrO2、CeO2、および、RuO2を用意し、Ba: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1~24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25~28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、BaCO3、CeO2、Y2O3、および、RuO2を用意し、Ba: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。この後、実施例1~24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29~32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、BaCO3、CeO2、および、RuO2を用意し、Ba: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1~24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33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、BaCO3、ZrO2、CeO2、および、RuO2を用意し、Ba: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。この混合物におけるBa:Zr:Ce:Ruのモル比は、実施例26の炭化水素改質触媒を作製する際に用いた材料のBa:Zr:Ce:Ruのモル比と同じである。この後、焼成温度を500℃とした以外は、実施例26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。比較例1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、BaCO3、ZrO2、CeO2、Y2O3、および、RuO2を用意し、Ba: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Ba:Zr:Ce:Y:Ruのモル比は、実施例2の炭化水素改質触媒を作製する際に用いた材料のBa:Zr:Ce:Y:Ruのモル比と同じである。この後、焼成温度を500℃とした以外は、実施例2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。
上述した実施例1~33および比較例1~2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1~33の炭化水素改質触媒と、比較例1~2の炭化水素改質触媒を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Ru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1~33および比較例1~2の炭化水素改質触媒をそれぞれ粉砕、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。
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487cc/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。表2に、各実施例および比較例の炭化水素改質触媒を用いた場合に、硫黄存在下において、1時間後にガス排出管5から排出された水素の濃度と平衡到達率を示す。表2では、「硫黄劣化後」の水素濃度、および、「硫黄劣化後の平衡到達率」と表記している。硫黄劣化後の平衡到達率は、次式(4)により定義した。
硫黄劣化後の平衡到達率=硫黄劣化後の水素濃度/平衡水素濃度×100 (4)
上記硫黄劣化後の特性確認後、管1に、窒素(N2)を360cc/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700℃まで加熱し、そのまま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360cc/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。
加熱による回復率=(加熱処理後の水素濃度-硫黄劣化後の水素濃度)/平衡水素濃度×100 (5)
表2に示すように、本発明の要件を満たす実施例1~33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67%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1~2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37%以下と低い値になった。
表2に示すように、本発明の要件を満たしていない比較例1~2の炭化水素改質触媒を用いた場合には、硫黄劣化後の平衡到達率が0%となった。これに対して、本発明の要件を満たす実施例1~33の炭化水素改質触媒を用いた場合、硫黄劣化後の平衡到達率は19%以上となった。本発明の要件を満たす炭化水素改質触媒では、Ru成分が複合酸化物に固溶分散しているため結合力が強く、硫黄などの被毒成分の吸着や化合物の生成を抑制する効果が得られ、高い硫黄耐久性を有するものと考えられる。
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のうち、複合酸化物にYが含まれる実施例1~24および29~32の炭化水素改質触媒を用いた場合、加熱による回復率が0%より高い値となった。すなわち、それらの炭化水素改質触媒では、加熱処理によって、硫黄劣化した触媒機能が回復した。
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 (11)
- 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、BaCeO3を主成分とする結晶相を有し、かつ、Ruを含み、
前記複合酸化物に含まれるBaに対するRuのモル比は、0.04以上0.43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、BaZrO3を主成分とする結晶相をさらに有することを特徴とする請求項1に記載の炭化水素改質触媒。
- 前記ペロブスカイト構造は、少なくともBa、Zr、Ce、および、Ruにより構成されてい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。
- 前記複合酸化物にYが含まれておらず、
Baに対するCeのモル比は、0.50以上0.70以下であることを特徴とする請求項1~3のいずれかに記載の炭化水素改質触媒。 - 前記複合酸化物にYが含まれ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。
- 前記ペロブスカイト構造は、少なくともBa、Zr、Ce、Y、および、Ruにより構成されていることを特徴とする請求項5に記載の炭化水素改質触媒。
- 前記Baに対する前記Ceのモル比は、0.10以上0.70以下であることを特徴とする請求項6に記載の炭化水素改質触媒。
- 前記Baに対する前記Ruのモル比は、0.08以上0.43以下であることを特徴とする請求項1~7のいずれかに記載の炭化水素改質触媒。
- 前記Baに対する前記Yのモル比は、0.05以上0.50以下であることを特徴とする請求項6~8のいずれかに記載の炭化水素改質触媒。
- 前記Baに対する、前記Zrと前記Ceと前記Yの合計量のモル比は、0.71以上1.67以下であることを特徴とする請求項6~9のいずれか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1~10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。
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