JP7485882B2 - 水素生成装置およびそれを用いた燃料電池システム並びにその運転方法 - Google Patents
水素生成装置およびそれを用いた燃料電池システム並びにその運転方法 Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims description 282
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 282
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 280
- 239000000446 fuel Substances 0.000 title claims description 81
- 238000000034 method Methods 0.000 title claims description 14
- 239000007789 gas Substances 0.000 claims description 244
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 232
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 201
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 155
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 155
- 229910021529 ammonia Inorganic materials 0.000 claims description 116
- 239000002994 raw material Substances 0.000 claims description 93
- 238000007254 oxidation reaction Methods 0.000 claims description 65
- 239000003054 catalyst Substances 0.000 claims description 59
- 230000003647 oxidation Effects 0.000 claims description 54
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 27
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 230000008859 change Effects 0.000 claims description 20
- 230000005611 electricity Effects 0.000 claims description 12
- 238000006057 reforming reaction Methods 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 197
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 110
- 239000003345 natural gas Substances 0.000 description 97
- 229910052757 nitrogen Inorganic materials 0.000 description 55
- 239000000126 substance Substances 0.000 description 29
- 238000000354 decomposition reaction Methods 0.000 description 27
- 230000001590 oxidative effect Effects 0.000 description 26
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 23
- 238000000629 steam reforming Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 239000002737 fuel gas Substances 0.000 description 12
- 238000004364 calculation method Methods 0.000 description 10
- 238000002407 reforming Methods 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- -1 naphtha Substances 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Description
図1は、実施の形態1における水素生成装置の構成を示すブロック図である。
次に、実施の形態2について説明する。
20 原料供給器
30 水供給器
31 蒸発器
40 酸化ガス供給器
50 改質器温度検知器
60 水素含有ガス供給流路
61 水素含有ガス供給流路
70 燃料ガス供給流路
100 改質器
120 変成器
125 変成器温度検知器
130 変成器加熱器
150 CO除去器
200 燃料電池
300,301 制御器
310,311 情報取得器
350 水素生成装置
400 燃料電池システム
Claims (8)
- 炭化水素系の原料から改質反応により水素含有ガスを生成する改質器と、
酸化触媒を有し、前記酸化触媒を用いて前記水素含有ガスに含まれる一酸化炭素の濃度を酸化反応により低減し、前記水素含有ガスに含まれるアンモニアを分解するCO除去器と、
前記改質器に前記原料を供給する原料供給器と、
前記改質器に前記改質反応に用いられる水を供給する水供給器と、
前記CO除去器に酸化ガスを供給する酸化ガス供給器と、
前記改質器を加熱する加熱器と、
制御器と、を備え、
前記制御器は、前記CO除去器に供給される前記水素含有ガスのアンモニア濃度に関するパラメータを基に、前記CO除去器に供給される前記水素含有ガスの水蒸気分圧の上限値を決定し、前記水蒸気分圧の設定値が前記上限値より低い値となるように前記設定値を変更することを特徴とする、水素生成装置。 - 前記制御器は、前記設定値を変更するために、
前記原料供給器から供給される原料供給量を前記原料に窒素化合物が含まれていない場合の運転時の原料供給量である第一原料供給量より高い値に変更するように前記原料供給器を制御する原料増量動作と、
前記水供給器から供給される水供給量を前記原料に窒素化合物が含まれていない場合の運転時の水供給量である第一水供給量より低い値に変更するように前記水供給器を制御する水減量動作と、
前記改質器の温度を前記原料に窒素化合物が含まれていない場合の運転時の温度である第一設定温度より高い値に変更するように前記加熱器を制御する加熱動作と、
のうち少なくとも一つの動作を行うことを特徴とする、請求項1に記載の水素生成装置。 - 前記改質器により生成された前記水素含有ガス中の一酸化炭素濃度を水性ガスシフト反応により低減する変成器と、
前記変成器を加熱する変成器加熱器と、をさらに備え、
前記制御器は、前記パラメータに応じて、前記変成器の出口部の温度を、前記原料に窒素化合物が含まれていない場合の運転時の温度である第一変成温度より低い値に変更するように前記変成器加熱器を制御することを特徴とする、請求項1または2に記載の水素生成装置。 - 前記制御器は、前記パラメータを、前記原料の窒素化合物の濃度に関連する情報を基に決定するよう構成されていることを特徴とする、請求項1から3のいずれか1項に記載の水素生成装置。
- 前記情報を取得する情報取得器をさらに備えていることを特徴とする、請求項4に記載の水素生成装置。
- 前記情報は、窒素化合物の濃度に係る情報、前記原料の種類に係る情報、位置情報、および、前記原料の供給主体から得られた情報のうち少なくとも一つを含むことを特徴とする、請求項4または5記載の水素生成装置。
- 請求項1から6のいずれか1項に記載の水素生成装置と、
前記水素生成装置から供給される水素含有ガスを用いて発電する燃料電池と、
を備えた燃料電池システム。 - 炭化水素系の原料から改質反応により水素含有ガスを生成する改質器と、
酸化触媒を有し、前記酸化触媒を用いて前記水素含有ガスに含まれる一酸化炭素の濃度を酸化反応により低減し、前記水素含有ガスに含まれるアンモニアを分解するCO除去器と、
前記改質器に前記原料を供給する原料供給器と、
前記改質器に前記改質反応に用いられる水を供給する水供給器と、
前記CO除去器に酸化ガスを供給する酸化ガス供給器と、
前記改質器を加熱する加熱器と、
を備えた水素生成装置の運転方法であって、
前記CO除去器に供給される前記水素含有ガスのアンモニア濃度に関するパラメータを基に、前記CO除去器に供給される前記水素含有ガスの水蒸気分圧の上限値を決定し、前記水蒸気分圧の設定値が前記上限値より低い値となるように前記設定値を変更することを特徴とする、水素生成装置の運転方法。
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