JP5530774B2 - 重質炭化水素油の分解方法 - Google Patents
重質炭化水素油の分解方法 Download PDFInfo
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- JP5530774B2 JP5530774B2 JP2010064931A JP2010064931A JP5530774B2 JP 5530774 B2 JP5530774 B2 JP 5530774B2 JP 2010064931 A JP2010064931 A JP 2010064931A JP 2010064931 A JP2010064931 A JP 2010064931A JP 5530774 B2 JP5530774 B2 JP 5530774B2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000003921 oil Substances 0.000 description 86
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000005336 cracking Methods 0.000 description 9
- -1 monocyclic aromatic compounds Chemical class 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 5
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
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- 238000004611 spectroscopical analysis Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 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
- 238000009826 distribution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910001119 inconels 625 Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Description
水の存在下で重量平均分子量が500以上の重質炭化水素油を触媒に接触させて軽質炭化水素油を製造する重質炭化水素油の分解方法であって、
前記触媒が、第4A族元素とAl 2 O 3 との複合酸化物であり、第4A族元素を20質量%以上の量で含有し、前記軽質炭化水素油の重量平均分子量が前記重質炭化水素油の半分以下であることを特徴とする。
また、前記第4A族元素はチタンまたはジルコニウムであるのが望ましい。
本発明の重質炭化水素油の分解方法は、
水の存在下で重量平均分子量が500以上の重質炭化水素油を触媒に接触させて軽質炭化水素油を製造する重質炭化水素油の分解方法であって、
前記触媒が第4A族元素を10質量%以上の量で含有し、かつ前記軽質炭化水素油の重量平均分子量が前記重質炭化水素油の半分以下であることを特徴としている。
なお、本明細書において重量平均分子量とは、ゲル浸透クロマトグラフィー(GPC)によるポリスチレン換算値を意味する。
TiO2(MC‐90、石原産業(株)製)50gに対し、試薬の硝酸アルミニウム(Al(NO3)3・9H2O)36.78gをイオン交換水に溶解させて77mlの水溶液とし、磁性皿にてTiO2にAl2O3を担持させてスラリー状とした。次いで機械的に混合した後、室温にて1時間静置し、さらに130℃に設定した乾燥機で、途中数回にわたって塊状沈殿物を溶解しながら1昼夜乾燥し、平均粒径300μm以下に整粒した乾燥重量57.38gの触媒原料を得た。
ZrO2(XZO631/05、MEL製)80gに対し、試薬の硝酸アルミニウム(Al(NO3)3・9H2O)42.7gをイオン交換水に溶解させて55mlの水溶液とし、磁性皿にてZrO2にAl2O3を担持させてスラリー状とした。次いで機械的に混合した後、室温にて1時間静置し、さらに130℃に設定した乾燥機で、途中数回にわたって塊状沈殿物を溶解しながら1昼夜乾燥し、平均粒径300μm以下に整粒した乾燥重量57.38gの触媒原料を得た。
Al2O3(γ−アルミナ、和光純薬工業(株)製)50gに対し、試薬のTiO2(30%硫酸チタン溶液)20.0gをイオン交換水に溶解させて63mlの水溶液とし、磁性皿にてAl2O3にTiO2を担持させてスラリー状とした。次いで機械的に混合した後、室温にて1時間静置し、さらに130℃に設定した乾燥機で、途中数回にわたって塊状沈殿物を溶解しながら1昼夜乾燥し、平均粒径300μm以下に整粒した乾燥重量57.84gの触媒原料を得た。
得られた触媒A〜Cの組成を表1に示す。
超合金(インコネル625)製の反応器(内容積10ml)中に、触媒Aを6.0mL充填した。次いで、触媒Aを充填した反応器内にイオン交換水を30.0mL/hで流通させつつ温度:470℃、圧力:28MPaまで加熱及び加圧した後、水素を添加することなく、表2に示す組成の重質炭化水素油(石油系常圧残油、重量平均分子量=1,500)を6.0ml/hの速度で反応器内に投入した。なお、重量平均分子量は、ゲル浸透クロマトグラフィー(装置:アジレント1100、カラム:PL 3μm Guard (7.5×50mm)+ 3μm Mixed-E (7.5×300mm 2本))を用いてポリスチレン換算値により求めた。
触媒Bを用いた以外、実施例1に従って生成油を採取し、蒸留性状を分析した。結果を表2に示す。
触媒Cを用いた以外、実施例1に従って生成油を採取し、蒸留性状を分析した。結果を表2に示す。
Claims (2)
- 水の存在下で重量平均分子量が500以上の重質炭化水素油を触媒に接触させて軽質炭化水素油を製造する重質炭化水素油の分解方法であって、
前記触媒が、第4A族元素とAl 2 O 3 との複合酸化物であり、第4A族元素を20質量%以上の量で含有し、前記軽質炭化水素油の重量平均分子量が前記重質炭化水素油の半分以下であることを特徴とする重質炭化水素油の分解方法。 - 前記第4A族元素が、チタンまたはジルコニウムであることを特徴とする請求項1に記載の重質炭化水素油の分解方法。
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JP2010064931A JP5530774B2 (ja) | 2010-03-19 | 2010-03-19 | 重質炭化水素油の分解方法 |
CA2793813A CA2793813A1 (en) | 2010-03-19 | 2011-03-10 | Heavy hydrocarbon oil cracking catalyst and method for cracking heavy hydrocarbon oil |
PCT/JP2011/001417 WO2011114670A1 (ja) | 2010-03-19 | 2011-03-10 | 重質炭化水素油分解用触媒及び重質炭化水素油の分解方法 |
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JP5530774B2 true JP5530774B2 (ja) | 2014-06-25 |
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JPH0625676A (ja) * | 1992-07-08 | 1994-02-01 | Cosmo Sogo Kenkyusho:Kk | 重質油の流動接触分解法 |
JP3479783B2 (ja) * | 1993-12-29 | 2003-12-15 | 東燃ゼネラル石油株式会社 | 重質油の流動接触分解触媒用添加剤 |
JPH09285728A (ja) * | 1996-04-23 | 1997-11-04 | Tonen Corp | 重質油分解用添加剤及び重質油の流動接触分解用触媒 |
JP4508381B2 (ja) * | 1999-08-25 | 2010-07-21 | メタウォーター株式会社 | 有機廃棄物分解用酸化鉄系触媒、その製造方法及び有機廃棄物の処理方法 |
JP2002129171A (ja) * | 2000-10-27 | 2002-05-09 | Ngk Insulators Ltd | 重質油の分解方法 |
JP4780273B2 (ja) * | 2004-06-29 | 2011-09-28 | メタウォーター株式会社 | 重質油を軽質化するための触媒の製造方法 |
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