JP5243860B2 - 水素製造方法 - Google Patents
水素製造方法 Download PDFInfo
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- JP5243860B2 JP5243860B2 JP2008168971A JP2008168971A JP5243860B2 JP 5243860 B2 JP5243860 B2 JP 5243860B2 JP 2008168971 A JP2008168971 A JP 2008168971A JP 2008168971 A JP2008168971 A JP 2008168971A JP 5243860 B2 JP5243860 B2 JP 5243860B2
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- hydrogen
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- dehydrogenation
- hydride
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- 229910052739 hydrogen Inorganic materials 0.000 title claims description 130
- 239000001257 hydrogen Substances 0.000 title claims description 130
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 98
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 78
- 239000003054 catalyst Substances 0.000 claims description 76
- 150000002431 hydrogen Chemical class 0.000 claims description 33
- -1 aromatic hydrocarbon hydride Chemical class 0.000 claims description 30
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 19
- 150000004678 hydrides Chemical class 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 description 28
- 239000012528 membrane Substances 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 15
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 239000007809 chemical reaction catalyst Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CKENDVLIAVMNDW-UHFFFAOYSA-N 1,2-dimethyl-4-phenylbenzene Chemical group C1=C(C)C(C)=CC=C1C1=CC=CC=C1 CKENDVLIAVMNDW-UHFFFAOYSA-N 0.000 description 4
- 229910002668 Pd-Cu Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002683 reaction inhibitor Substances 0.000 description 3
- 238000011084 recovery Methods 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
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000001934 cyclohexanes Chemical class 0.000 description 2
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000001179 sorption measurement 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
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-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
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 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
- 230000006698 induction Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping 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
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Description
脱水素反応触媒として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%)を前述の脱水素反応器3に充填した。ここで、触媒層の容積は1.4Lとした。そして、最初に、脱水素反応器3の触媒層を250℃の熱風で加熱しながら触媒層に水素のみを0.5Nm3/hの条件で30分供給した。その後、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0.3MPaG、液空間速度(LHSV)=2.0hr−1、水素/オイル比(H2/Oil)=1.0mol/molの条件でMCHおよび水素の混合物を触媒層に連続的に流通して水素を製造した。MCHの通油開始から30分後(運転開始から1時間後)に、熱風の温度を10℃/minの速度で250℃から430℃まで昇温した。運転開始2時間後から5時間後まで1時間置きに気液分離後の回収油を採取し、水素化反応の阻害物質となる3、4ジメチルビフェニル含量を測定した。なお、3、4ジメチルビフェニル含量の測定は、生成油のGC−MS分析(Agilent社製GC−6890N)にて行った。また、触媒層中央部に挿入した保護管の内部に設置した熱電対で測定した、触媒層を反応器入口側の部分、中間の部分、反応器出口側の部分に三等分した場合の各部の中央にあたる位置の温度から触媒層の平均温度を算出した。
熱風温度を運転開始時から430℃で一定とした以外は、参考例1と同様にして、脱水素反応を行った。
2 タンク
3 脱水素反応器
4 水素分離装置
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う水素の製造方法であって、
前記触媒層に水素を供給する工程と、
前記触媒層を第1の温度まで加熱する工程と、
水素が供給され前記第1の温度まで加熱された触媒層に、芳香族炭化水素の水素化物を供給して該水素化物の脱水素反応を開始させる工程と、
前記水素および前記芳香族炭化水素の水素化物が供給されている触媒層を、前記第1の温度より高い第2の温度まで加熱する工程と、
を含み、
前記触媒層を前記第2の温度まで加熱し始めるタイミングは、前記芳香族炭化水素の水素化物の前記触媒層への流通を検知したタイミングとする、
水素製造方法。 - 前記第2の温度が、200℃以上340℃以下であることを特徴とする、請求項1に記載の水素製造方法。
- 前記第1の温度が、前記第2の温度より20〜100℃低いことを特徴とする、請求項1または請求項2に記載の水素製造方法。
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JP5243860B2 true JP5243860B2 (ja) | 2013-07-24 |
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JP5737853B2 (ja) * | 2010-03-29 | 2015-06-17 | 千代田化工建設株式会社 | 貯蔵・輸送用水素の製造方法 |
WO2014157133A1 (ja) * | 2013-03-25 | 2014-10-02 | Jx日鉱日石エネルギー株式会社 | 水素供給システムの運転方法、水素供給設備及び水素供給システム |
JP6246027B2 (ja) | 2014-03-10 | 2017-12-13 | 千代田化工建設株式会社 | 水素製造システムおよび水素製造方法 |
JP6669549B2 (ja) * | 2016-03-24 | 2020-03-18 | 千代田化工建設株式会社 | 触媒、触媒の製造方法、及び触媒を使用した水素の製造方法 |
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JP4201119B2 (ja) * | 2002-10-22 | 2008-12-24 | 勝 市川 | 水素貯蔵・供給システム |
JP2005035842A (ja) * | 2003-07-15 | 2005-02-10 | Nippon Oil Corp | 水素製造システム |
JP4652695B2 (ja) * | 2004-01-30 | 2011-03-16 | 千代田化工建設株式会社 | 水素化芳香族類の脱水素触媒及びその製造方法 |
JP4684069B2 (ja) * | 2005-09-30 | 2011-05-18 | Jx日鉱日石エネルギー株式会社 | 高純度水素の製造方法 |
JP4907210B2 (ja) * | 2006-03-30 | 2012-03-28 | 千代田化工建設株式会社 | 水素の貯蔵輸送システム |
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