CN1285390A - 含氧气体的预重整方法 - Google Patents
含氧气体的预重整方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000001301 oxygen Substances 0.000 title claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 17
- 239000007789 gas Substances 0.000 title description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- 238000002407 reforming Methods 0.000 claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 6
- 238000001193 catalytic steam reforming Methods 0.000 claims abstract description 5
- 239000011029 spinel Substances 0.000 claims abstract description 5
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 8
- 229910020068 MgAl Inorganic materials 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910026161 MgAl2O4 Inorganic materials 0.000 abstract 1
- 238000000629 steam reforming Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 239000001273 butane Substances 0.000 description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 238000006057 reforming reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 239000003915 liquefied petroleum gas Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 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
- 239000007864 aqueous solution Substances 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LBDSXVIYZYSRII-IGMARMGPSA-N alpha-particle Chemical compound [4He+2] LBDSXVIYZYSRII-IGMARMGPSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
本发明公开了一种含有高级烃和氧气的烃原料的催化蒸汽重整方法,其包括原料的催化预重整和预重整原料的蒸汽重整步骤,预重整步骤在固定床催化剂存在下进行,所述催化剂含有至少一部分在烃氧化为碳的氧化物和高级烃转化为甲烷过程中是活泼的贵金属催化剂,其中贵金属催化剂承载于MgO和/或MgAl2O4尖晶石载体上。
Description
本发明涉及含有氧气的工艺过程的气体，例如天然气、峰削平气体(peak shaving gas)、液化石油气(LPG)等的预重整方法。预重整是在生产富氢气和/或一氧化碳气体中催化蒸汽重整之前进行的过程。在预重整步骤中，高级烃物质转化为甲烷，甲烷重整反应(1)和水煤气轮换反应平衡接近于操作温度。
在上述过程原料气体中的氧气导致烃的氧化脱水，产生烯烃。预重整催化剂对于气体中的烯烃浓度是关键的，当浓度超过某关键值时将形成碳。
在过渡金属催化剂和贵金属催化剂存在下烃原料与水或二氧化碳在氧气存在下的部分氧化在WO99/35082中提及。
本发明的一般目的是改善含有氧气的烃原料的催化蒸汽重整的已知方法，包括原料的催化预重整步骤而不在预重整催化剂上明显形成有害的碳。
更具体地说，本发明利用贵金属催化剂，它在使用惰性气体中可获得的氧气的催化氧化中是活泼的以氧化烃形成一氧化碳，例如(3)和二氧化碳，例如(4)，并且具有作为将高级烃转化为甲烷的预重整催化剂的活性和平衡甲烷重整反应(1)和水煤气轮换反应(2)。
在预重整器的入口处放热催化氧化反应3和4是主要的反应，为随后的反应释放热量，根据原料气体中的氧气含量导致工艺气体的温度增加。当工艺气体中的氧气含量被上述反应3和4消耗时，吸热的甲烷重整反应将是主要的反应，导致过程温度下降。由于通过催化燃烧反应3和4产生热量，与入口原料中没有氧气的蒸汽重整过程相比出口气体将具有较高的温度和较高的甲烷重整平衡温度。随后的蒸汽重整步骤因而需要较少负荷以在蒸汽重整步骤的流出气体中得到相同数量的氢气和/或一氧化碳。
根据上述观察，本发明提供了含有高级烃和氧气的烃原料的催化蒸汽重整方法，其包括原料的催化预重整和预重整原料的蒸汽重整步骤。预重整步骤在固定床催化剂存在下进行，所述催化剂含有至少一部分在烃氧化为碳的氧化物和高级烃转化为甲烷过程中是活泼的贵金属催化剂。贵金属催化剂承载于MgO和/或MgAl2O4尖晶石载体上。
用于氧化催化剂中的合适金属包括至少一种选自周期表第Ⅷ族的贵金属，它承载于氧化铝、氧化镁、二氧化钛、二氧化硅、氧化锆、氧化铍、氧化钍、氧化镧、氧化钙或它们的混合物的催化剂载体上。
用于本发明方法的含有贵金属的催化剂通过现有技术中常规使用的任何方法制备，包括用含有贵金属的水溶液浸渍载体物质和在空气中焙烧所浸渍的物质。
载体物质通常选自氧化铝、氧化镁、二氧化钛、二氧化硅、氧化锆、氧化铍、氧化钍、氧化镧、氧化钙和它们的混合物。优选的载体物质是镁，氧化铝尖晶石和氧化镁。
贵金属催化剂通常作为固定床放置在预重整反应器中。
在预重整反应器中，贵金属催化剂选择性地用作常规预重整催化剂上的顶层。
本发明进一步用如下实施例说明。
实施例1
颗粒尺寸为4.5mm的MgO和MgAl2O4尖晶石的催化剂载体物质用含有按重量计约3％Rh的硝酸铑水溶液浸渍，随后在750℃焙烧，从而硝酸盐分解为氧化物。
上述制备的催化剂以固定床方式放置在反应管中，床体积为74.5ml，相当于58.4g催化剂。反应管放置在五区域电加热烘箱中以保持在实验中基本上等温温度分布型。
烘箱和入口管线在氮气流中加热。当达到预定的操作温度时，加入蒸汽，用相应于表1中给出的组成的预混合的天然气-空气混合物和丁烷流置换氮气。
表1
原料的组成，C2H6+表示所有具有2个和更多个碳原子的烃。
| CH4 C2H6+ N2 CO2 O2 Ar 丁烷 H2Ovol％ vol％ vol％ vol％ vol％ vol％ vol％ vol％ |
| 13.34 0.69 5.68 0.17 1.11 0.06 3.97 74.99 |
总流量为约380Nl/h，相当于约5000h-1的空速。
实验在450℃和480℃的烘箱温度下进行。两种实验显示在原料气体中氧气完全转化，丁烷接近完全转化为甲烷(在出口处丁烷为0-580ppmv，干基)。同时，甲烷重整反应和转移反应的平衡在烘箱温度的10℃之内。
可以观察到，在存在氧气时由于发生放热催化氧化反应，在反应器的顶部存在比给定温度高的高温区域，该区域之后是比给定温度低的低温区域，向给定温度缓慢增加。这是由于吸热甲烷重整反应引起的。
实施例2
含有约10wt％α-氧化铝和颗粒尺寸为4.5×4.5mm的MgAl2O4催化剂载体用含有按重量计约2％Rh的硝酸铑水溶液浸渍，随后在750℃焙烧，从而硝酸盐分解为氧化物。
该催化剂以固定床方式放置在反应管中，床体积为74.5ml，含有79.8g上述制备的催化剂。反应管放置在五区域电加热烘箱中以保持在实验中基本上等温温度分布型。
烘箱和入口管线在氮气流中加热。当达到操作温度时，加入蒸汽，用相应于表2中给出的组成的预混合的天然气-空气混合物和丁烷流置换氮气。
表2
原料的组成，C2H6+表示所有含有2个和更多个碳原子的烃。
| CH4 C2H6+ N2 CO2 O2 Ar 丁烷 H2Ovol％ vol％ vol％ vol％ vol％ vol％ vol％ vol％ |
| 13.34 0.69 5.68 0.17 1.11 0.06 3.97 74.99 |
总流量为约380Nl/h，得到约5000h-1的空速。
实验在450℃的烘箱温度下进行。实验显示氧气完全转化，丁烷完全转化为甲烷。同时，甲烷重整反应的平衡在烘箱温度的15℃之内，而转移反应具有约-20℃至-60℃的负值(negativeapproach)，表示组成的平衡温度高于反应器温度。
在入口处由于放热反应消耗氧气，反应器内的温度分布型显示比反应器的调定点高的温度。在该区域下方，由于吸热的重整反应温度降低至给定温度附近。
Claims (4)
1．一种含有高级烃和氧气的烃原料的催化蒸汽重整方法，其包括原料的催化预重整和预重整原料的蒸汽重整步骤，预重整步骤在固定床催化剂存在下进行，所述催化剂含有至少一部分在烃氧化为碳的氧化物和高级烃转化为甲烷过程中是活泼的贵金属催化剂，其中贵金属催化剂承载于MgO和/或MgAl2O4尖晶石载体上。
2．权利要求1的方法，其中贵金属催化剂含有至少一种周期表第Ⅷ族的贵金属。
3．权利要求2的方法，其中贵金属催化剂是铑。
4．根据上述权利要求中任一项的方法，其中贵金属催化剂作为顶层放置在固定床催化剂中。
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| US6981994B2 (en) * | 2001-12-17 | 2006-01-03 | Praxair Technology, Inc. | Production enhancement for a reactor |
| JP2004079262A (ja) * | 2002-08-13 | 2004-03-11 | Mitsubishi Heavy Ind Ltd | 水素供給システム及び移動式水素製造装置 |
| US6977067B2 (en) * | 2003-02-12 | 2005-12-20 | Engelhard Corporation | Selective removal of olefins from hydrocarbon feed streams |
| US7427388B2 (en) | 2004-03-19 | 2008-09-23 | Air Products And Chemicals, Inc. | Process for improving prereforming and reforming of natural gas containing higher hydrocarbons along with methane |
| TWI398406B (zh) * | 2005-09-21 | 2013-06-11 | Nippon Oil Corp | Automatic starting method of thermal reformer |
| JP5224651B2 (ja) | 2006-03-31 | 2013-07-03 | Ｊｘ日鉱日石エネルギー株式会社 | 固体酸化物形燃料電池 |
| JP4933818B2 (ja) | 2006-04-07 | 2012-05-16 | Ｊｘ日鉱日石エネルギー株式会社 | 固体酸化物形燃料電池システムの運転方法 |
| US7365102B1 (en) | 2007-02-26 | 2008-04-29 | Delphi Technologies, Inc. | Process for pre-reforming hydrocarbon fuels |
| US8323365B2 (en) | 2007-05-22 | 2012-12-04 | Praxair Technology, Inc. | Dual mode reactor SMR integration |
| US8808654B2 (en) | 2009-09-29 | 2014-08-19 | Praxair Technology, Inc. | Process for sulfur removal from refinery off gas |
| US9116528B2 (en) | 2011-04-26 | 2015-08-25 | Panasonic Intellectual Property Management Co., Ltd. | Hydrogen generation apparatus, fuel cell system, and method of operating the same |
| EP2703340B1 (en) | 2011-04-26 | 2017-07-19 | Panasonic Intellectual Property Management Co., Ltd. | Hydrogen generation apparatus and fuel cell system |
| BR102021007738A2 (pt) | 2021-04-22 | 2022-11-01 | Petróleo Brasileiro S.A. - Petrobras | Método de manutenção da atividade de catalisadores de pré-reforma |
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| JPS5274591A (en) * | 1975-12-17 | 1977-06-22 | Nippon Soken | Catalysts for reforming hydrocarbon fuels |
| US4844837A (en) * | 1982-09-30 | 1989-07-04 | Engelhard Corporation | Catalytic partial oxidation process |
| JPS63248444A (ja) * | 1987-04-03 | 1988-10-14 | Tokyo Gas Co Ltd | 炭化水素の水蒸気改質および／または部分酸化用触媒 |
| JPH0733242B2 (ja) * | 1988-12-15 | 1995-04-12 | 川崎重工業株式会社 | 燃料電池用燃料改質方法 |
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| GB9806199D0 (en) * | 1998-03-24 | 1998-05-20 | Johnson Matthey Plc | Catalytic generation of hydrogen |
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