JP5215057B2 - 水素製造方法 - Google Patents
水素製造方法 Download PDFInfo
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- JP5215057B2 JP5215057B2 JP2008169025A JP2008169025A JP5215057B2 JP 5215057 B2 JP5215057 B2 JP 5215057B2 JP 2008169025 A JP2008169025 A JP 2008169025A JP 2008169025 A JP2008169025 A JP 2008169025A JP 5215057 B2 JP5215057 B2 JP 5215057B2
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- 229910052739 hydrogen Inorganic materials 0.000 title claims description 205
- 239000001257 hydrogen Substances 0.000 title claims description 205
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 108
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 150000002431 hydrogen Chemical class 0.000 claims description 100
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 99
- 238000000926 separation method Methods 0.000 claims description 82
- 239000012528 membrane Substances 0.000 claims description 60
- 239000003054 catalyst Substances 0.000 claims description 32
- -1 aromatic hydrocarbon hydride Chemical class 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 description 28
- 238000011084 recovery Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000000446 fuel Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000012466 permeate Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000007809 chemical reaction catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229910002668 Pd-Cu Inorganic materials 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- NHCREQREVZBOCH-UHFFFAOYSA-N 1-methyl-1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene Chemical compound C1CCCC2C(C)CCCC21 NHCREQREVZBOCH-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001934 cyclohexanes Chemical class 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- GCYUJISWSVALJD-UHFFFAOYSA-N 1,1-diethylcyclohexane Chemical compound CCC1(CC)CCCCC1 GCYUJISWSVALJD-UHFFFAOYSA-N 0.000 description 1
- HUMCBDCARGDFNV-UHFFFAOYSA-N 1-ethyl-1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene Chemical compound C1CCCC2C(CC)CCCC21 HUMCBDCARGDFNV-UHFFFAOYSA-N 0.000 description 1
- FUUGBGSHEIEQMS-UHFFFAOYSA-N 4a,8a-dimethyl-1,2,3,4,5,6,7,8-octahydronaphthalene Chemical compound C1CCCC2(C)CCCCC21C FUUGBGSHEIEQMS-UHFFFAOYSA-N 0.000 description 1
- DBDVZSFEBSXURB-UHFFFAOYSA-N C(C)C12CCCCC2(CCCC1)CC Chemical compound C(C)C12CCCCC2(CCCC1)CC DBDVZSFEBSXURB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Hydrogen, Water And Hydrids (AREA)
Description
前記水素分離装置中の水素分離膜の温度が、前記脱水素反応器中の触媒層の平均温度よりも10〜100℃高いことを特徴とする。
図1に示すように、熱風(熱媒体)を、水素分離装置3を通過させた後、脱水素反応器2を通過させて、脱水素反応及び水素分離を行った。脱水素反応器2として固定床流通式反応装置を、また、脱水素触媒として0.5%Pt/Al2O3触媒(平均細孔径72.9Å、全細孔容量に占める40〜80Åの細孔容量の割合60%)を使用し、該触媒を固定床流通式反応装置に充填した。ここで、触媒層の容積は10cm3とした。芳香族炭化水素水素化物としてメチルシクロヘキサン(MCH)を用い、反応圧力0.5MPaG、液空間速度(LHSV)=2.0hr-1、水素/オイル比(H2/Oil)=1.0mol/molの条件下で脱水素反応を行い、脱水素反応器2からの出口ガスを、水素分離膜を具える水素分離装置3に通して水素を選択透過させた。なお、水素分離装置3の入口ゲージ圧力は、脱水素反応の反応圧力と同じ0.5MPaGであり、一方、出口ゲージ圧力は、0.0MPaGである。また、水素分離膜としては、Pd−Cu膜を使用した。450℃の熱風を、水素分離装置3を通過させた後、脱水素反応器2を通過させたところ、水素分離装置3中の水素分離膜の温度は350℃で、脱水素反応器2中の触媒層の平均温度は327.6℃となった。水素分離膜の透過ガスの流量及び該透過ガスの水素濃度、水素分離膜の非透過ガスを気液分離装置5により気液分離した後のガス分の流量(非透過ガス流量)及び該ガス分の水素濃度、水素回収率を表1に示す。
脱水素反応の反応圧力及び水素分離装置3の入口ゲージ圧力を表1に示す圧力にする以外は、実施例1と同様にして、脱水素反応及び水素分離を行った。結果を表1に示す。
図2に示すように、熱風(熱媒体)を、脱水素反応器2を通過させた後、水素分離装置3を通過させて、脱水素反応及び水素分離を行う以外は、実施例1と同様にして、脱水素反応及び水素分離を行った。結果を表1に示す。
脱水素反応の反応圧力及び水素分離装置の入口ゲージ圧力を表1に示す圧力にする以外は、比較例1と同様にして、脱水素反応及び水素分離を行った。結果を表1に示す。
2 脱水素反応器
3 水素分離装置
4 加熱手段
5 気液分離装置
6 回収油タンク
Claims (3)
- 触媒層を具える脱水素反応器中で芳香族炭化水素の水素化物の脱水素反応を行い、水素分離膜を具える水素分離装置により該脱水素反応生成物から水素を分離する水素製造方法において、
前記水素分離装置中の水素分離膜の温度が、前記脱水素反応器中の触媒層の平均温度よりも10〜100℃高いことを特徴とする水素製造方法。 - 前記脱水素反応器及び前記水素分離装置を加熱するための熱媒体を、前記水素分離装置を通過させた後に前記脱水素反応器を通過させることを特徴とする請求項1に記載の水素製造方法。
- 更に、前記脱水素反応器から排出された熱媒体を再加熱して、前記水素分離装置に供給することを特徴とする請求項2に記載の水素製造方法。
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WO2010087337A1 (ja) | 2009-02-02 | 2010-08-05 | 株式会社神戸製鋼所 | 形状測定装置 |
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WO2013025659A1 (en) | 2011-08-12 | 2013-02-21 | Mcalister Technologies, Llc | Reducing and/or harvesting drag energy from transport vehicles, includings for chemical reactors, and associated systems and methods |
WO2013025655A2 (en) | 2011-08-12 | 2013-02-21 | Mcalister Technologies, Llc | Systems and methods for providing supplemental aqueous thermal energy |
WO2014160301A1 (en) | 2013-03-14 | 2014-10-02 | Mcalister Technologies, Llc | Method and apparatus for generating hydrogen from metal |
JP5945521B2 (ja) * | 2013-05-29 | 2016-07-05 | Jxエネルギー株式会社 | 水素の製造方法及び水素の製造システム |
JP6198677B2 (ja) * | 2014-05-30 | 2017-09-20 | Jxtgエネルギー株式会社 | 水素供給システム |
JP2017001914A (ja) * | 2015-06-11 | 2017-01-05 | 富士電機株式会社 | 水素製造装置及び水素製造方法 |
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