CN107107017A - 甲烷转化为合成气的方法 - Google Patents
甲烷转化为合成气的方法 Download PDFInfo
- Publication number
- CN107107017A CN107107017A CN201680005054.4A CN201680005054A CN107107017A CN 107107017 A CN107107017 A CN 107107017A CN 201680005054 A CN201680005054 A CN 201680005054A CN 107107017 A CN107107017 A CN 107107017A
- Authority
- CN
- China
- Prior art keywords
- oxide
- nickel
- regeneration
- reative cell
- methane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 52
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 46
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 131
- 230000008929 regeneration Effects 0.000 claims abstract description 88
- 238000011069 regeneration method Methods 0.000 claims abstract description 88
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 73
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 61
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 47
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 41
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims description 17
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003426 co-catalyst Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 5
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 5
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 4
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 239000003054 catalyst Substances 0.000 abstract description 20
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 239000007789 gas Substances 0.000 description 43
- 229960004424 carbon dioxide Drugs 0.000 description 30
- 229910001868 water Inorganic materials 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000000571 coke Substances 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- 229910003452 thorium oxide Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000001568 sexual effect Effects 0.000 description 3
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910004369 ThO2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000035611 feeding Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000471 manganese heptoxide Inorganic materials 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical compound [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- DNNLEMIRRGUGOZ-UHFFFAOYSA-N oxygen(2-);thorium(4+) Chemical compound [O-2].[O-2].[Th+4] DNNLEMIRRGUGOZ-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/74—Iron group metals
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
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Abstract
提供了将甲烷转化为合成气的方法和系统。某些示例性方法和系统包括在反应室中使甲烷和二氧化碳与氧化镍催化剂反应,从而提供合成气和还原的镍物质。还原的镍物质可以通过在再生室中用空气氧化而再生,从而产生再生的氧化镍和热量。再生的氧化镍和热量可以返回到反应室以驱动合成气反应。
Description
相关申请的交叉引用
本申请要求2015年2月13日递交的US临时专利申请62/116,134号的优先权权益,其全部内容在此通过引用并入本文。
技术领域
本申请公开的主题涉及将甲烷转化为合成气体(合成气)的方法和系统。
背景技术
合成气体,也称为合成气,是含有氢气(H2)和一氧化碳(CO)的气体混合物。合成气还可以包括二氧化碳(CO2)。合成气是一种可用于众多应用的化学原料。例如,合成气可用于通过费-托方法制备液体烃,包括烯烃(例如乙烯(C2H4))。合成气也可用于制备甲醇(CH3OH)。
合成气通常由甲烷(CH4)大规模生成,例如通过蒸汽重整过程或通过使用氧气(O2)的氧化重整。现有的过程可能会有缺陷。例如,蒸汽重整过程可能受焦炭形成的影响,这可能需要周期性的催化剂再生。蒸汽重整过程也可能是高度吸热和能量密集的过程。用氧气进行氧化重整可能是高度放热的,因此可能导致有问题的放热。
将甲烷转化为合成气的另一种方法可以是自热重整。在自热重整中,根据化学方程式(1),一部分甲烷可与氧气燃烧以提供二氧化碳和水:
CH4+2O2→CO2+2H2O (1)
该燃烧反应是放热的并提供热量。另外部分的甲烷根据化学方程式(2)可用二氧化碳进行干式重整,和根据化学方程式(3)可用水进行蒸汽重整,以提供合成气:
CH4+CO2→2CO+2H2 (2)
CH4+H2O→CO+3H2 (3)
燃烧反应(1)提供的热量可以驱动吸热干式重整(2)和蒸汽重整(3)反应。与标准干式重整和蒸汽重整方法相比,以此方式能够降低能耗。
然而,如上所述的自热重整方法可能具有缺点。自燃重整可能需要在燃烧步骤中使用纯氧。纯氧可能是昂贵的原料。
因此,仍然需要用于将甲烷转化为合成气的改进方法和系统,包括避免需要纯氧作为原料的方法和系统,同时还降低总体能耗。
发明内容
本申请公开的主题提供了将甲烷转化为合成气的方法和系统,即用于从甲烷制备合成气的方法和系统。
在一个实施方案中,制备合成气的示例性方法可以包括提供反应室和再生室。反应室可以包括氧化镍。所述方法可以进一步包括将甲烷和二氧化碳进料到反应室中,从而使甲烷和二氧化碳与氧化镍接触以提供合成气和还原的镍物质。所述方法还可以包括将还原的镍物质从反应室移至再生室。所述方法还可以包括将空气进料到再生室,从而使空气与还原的镍物质接触以提供再生的氧化镍和热量。所述方法还可以包括将再生的氧化镍和热量从再生室移至反应室。
在一个实施方案中,用于将甲烷转化为合成气的示例性系统可以包括反应室、再生室和循环系统。反应室可以包括还原的镍物质。再生室可以包括再生的氧化镍。循环系统可以被配置为将还原的镍物质从反应室进料到再生室,并将再生的氧化镍从再生室进料到反应室。
在某些实施方案中,氧化镍可包括固体载体。所述固体载体可以包括选自氧化铝、氧化镁和氧化硅的氧化物。
氧化镍可以包括直径在约200μm和约400μm之间的颗粒。
在某些实施方案中,镍可包括助催化剂。所述助催化剂可以包括选自氧化镧(III)、氧化铈(III)、氧化铂(II)、氧化钡、氧化钙和氧化钾的氧化物。
在某些实施方案中,反应室中的温度可以在约650℃至约1050℃之间。反应室中的温度可以在约750℃至约850℃之间。在某些实施方案中,再生室中的温度可以在约450℃至约850℃之间。再生室中的温度可以在约550℃至约750℃之间。
在某些实施方案中,所述方法可以包括将CO2从再生室移到反应室。
在某些实施方案中,所述系统可包括提升管柱(riser column)。
附图说明
图1是示出可以结合根据本申请公开的主题将甲烷转化为合成气的方法使用的示例性系统的示意图。
图2是示出可以结合根据本申请公开的主题将甲烷转化为合成气的方法使用的示例性系统的另一示意图。
具体实施方式
本申请公开的主题提供了将甲烷转化为合成气体(合成气),即一氧化碳和氢气的混合物的方法和系统。如上所述,需要改进的方法和系统,其可以从甲烷提供合成气,而不需要昂贵的纯氧并且具有改善的能量效率。本申请公开的主题提供了其中甲烷与二氧化碳和氧化镍催化剂例如Ni基混合氧化物反应的方法和系统。反应可以在反应室中进行,其中一氧化碳、氢气和水与还原的镍物质一起形成。还原的镍物质可以涂覆有焦炭颗粒。还原的镍物质可以通过循环系统从反应室循环出来并进入再生室。空气可以进料到再生室中,还原的镍物质可以被燃烧以提供再生的氧化镍。镍物质上的焦炭颗粒也可以燃烧,产生二氧化碳和热量。然后,再生的氧化镍可以通过循环系统循环回到反应室,以催化甲烷进一步的反应。在再生室中产生的二氧化碳和热量也可以循环进入反应室,以驱动甲烷至合成气的反应。以这种方式,空气可以用作氧化剂而不是纯氧,并且可以减少总体能耗。本申请公开的方法和系统可以具有优于现有方法和系统的优点,如下所述,包括改进的效率、降低的能耗和降低的成本。
如本文所使用的,术语“约”或“近似”是指对于由本领域普通技术人员确定的特定值在可接受的误差范围内,这将部分地取决于如何测量或确定该值,即,测量系统的局限性。例如,“约”可以表示给定值的高达20%、高达10%、高达5%和/或高达1%的范围。
反应和再生步骤
甲烷与二氧化碳和氧化镍的反应可以描述为甲烷的氧化,并可以表示为根据化学方程式(4)的“反应步骤”:
2CH4+CO2+NiO→2CO+3H2+H2O+Ni.C* (4)
“NiO”表示通常的氧化镍,并不一定具体地代表镍(II)氧化物(NiO);NiO还可以代表Ni(III)氧化物(Ni2O3)以及混合的镍氧化物,例如Ni(II)和Ni(III)氧化物的混合物。“Ni.C*”代表通常的还原的镍物质,其可以涂覆有焦炭颗粒(碳的固体颗粒)。Ni.C*可以代表各种氧化态的镍,例如金属镍(Ni(0))或Ni(0)和Ni(II)的混合物,且存在各种量的焦炭。所述反应步骤可以提供一氧化碳、氢气、水和还原的镍物质的混合物。所述反应步骤可以是吸热的并且可以消耗热量。
还原的镍物质与氧气的反应可以描述为还原的镍物质的氧化,并可以表示为根据化学方程式(5)的“再生步骤”:
Ni.C*+O2→NiO+CO2 (5)
“O2”表示分子氧,但是应当理解,氧源不一定是纯氧,而是可以包括更多稀释的氧源,例如空气。再生步骤可以提供再生的氧化镍和二氧化碳。再生步骤可以是放热的并可产生热量。
根据化学方程式(4)的反应步骤和根据化学方程式(5)的再生步骤可以组合成一个整体化学过程(6):
2CH4+1.5O2→2CO+3H2+H2O (6)
由于氧化镍在反应步骤(4)中消耗并且在再生步骤(5)中再生,所以镍通过整个过程(6)再循环并且可以被催化地使用。
氧化镍
所使用的氧化镍可以包括镍(II)氧化物、镍(III)氧化物及其组合。氧化镍可以是混合的氧化镍,例如Ni(II)和Ni(III)氧化物的混合物。氧化镍可以包含一定量的金属镍,即Ni(0)。
氧化镍可以包括一种或多种另外的金属。在某些实施方案中,所述另外的金属可被描述为助催化剂。在某些实施方案中,所述另外的金属可以是当与氧化镍或其它镍物质结合时可以改变氧化镍或其它镍物质的氧化还原性质的金属。例如,所述另外的金属可以加速还原的镍物质氧化成氧化镍。将还原的镍物质氧化成氧化镍的加速可以减少系统中存在的金属镍(Ni(0))的量并且可以减少焦炭形成。在某些实施方案中,所述金属可以是当与氧化镍或其它镍物质结合时可以使镍物质更碱性的金属,这可以减少焦炭形成。
作为非限制性实例,氧化镍可以包括一种或多种选自如下的另外的金属氧化物:铬氧化物(例如Cr2O3)、锰氧化物(例如MnO、MnO2、Mn2O3或Mn2O7)、铜氧化物(例如CuO)、钨氧化物(例如WO3)、镧氧化物(例如La2O3(氧化镧(III)))、铈氧化物(例如Ce2O3(氧化铈(III)))、铂氧化物(例如PtO(氧化铂(II))、钍氧化物(例如ThO2氧化钍(Ⅳ))、钨氧化物(例如WO3(氧化钨(Ⅵ)))、铟氧化物(例如In2O3(氧化铟(III)))、钡氧化物(例如BaO)、钙氧化物(例如CaO)和钾氧化物(例如K2O)及其组合。在某些实施方案中,氧化镍可以包括助催化剂,所述助催化剂可以包括一种或多种选自氧化镧(III)、氧化铈(III)、氧化铂(II)、氧化钡、氧化钙和氧化钾的氧化物。在某些实施方案中,催化剂可包括两种、三种、四种或更多种不同金属(元素)的氧化物。
氧化镍可包括固体载体。也就是说,氧化镍可以是固体负载的。在某些实施方案中,固体载体可以包括各种金属盐、准金属氧化物和金属氧化物,例如氧化钛(钛氧化物)、氧化锆(锆氧化物)、氧化硅(硅氧化物)、氧化铝(铝氧化物)、氧化钍(钍氧化物)、氧化镁(镁氧化物)和氯化镁。在某些实施方案中,固体载体可包括氧化铝(Al2O3)、二氧化硅(SiO2)、氧化镁(MgO)或其组合。在某些实施方案中,固体载体可以包括氧化镧(III)(La2O3)。当氧化镍包括固体载体时,催化剂可以包含相对于催化剂总重量计总体约2重量%至约15重量%的量的镍,催化剂的其余部分可以是固体载体和任选地助催化剂。在某些实施方案中,所述催化剂可以包含相对于催化剂总重量计总体约8重量%至约10重量%的镍。在某些实施方案中,所述催化剂可以包含相对于催化剂总重量计总体约4重量%至约5重量%的助催化剂(另外的金属)。
在某些实施方案中,可以使用氧化镍,而无固体载体。就是说,可以使用本体氧化物形式的氧化镍。
当与固体载体或不与固体载体一起使用时,氧化镍可具有确定的粒度或直径。直径可以表征为颗粒分布的中值直径。在某些实施方案中,氧化镍可以包括直径在约150μm至约600μm之间的颗粒,例如直径约150μm、约200μm、约250μm、约300μm、约350μm、约400μm、约450μm、约500μm、约550μm或约600μm。在某些实施方案中,氧化镍可包括直径在约150μm至约350μm之间或约200μm至约400μm之间的颗粒。氧化镍可以是颗粒、丸粒和/或其它粒子的形式。
甲烷转化为合成气的系统和方法
为了说明而非限制的目的,图1和2是可以结合本申请所公开主题的方法使用的示例性系统的示意性代表。系统100,200可以包括反应室102,202和再生室104,204。反应室102,202可以包括还原的镍物质。再生室104,204可以包括再生的氧化镍。系统100,200可以进一步包括将反应室102,202和再生室104,204连接的循环系统。循环系统可以被配置为将还原的镍物质通过料流110,210从反应室102,202进料到再生室104,204,并将再生的氧化镍通过料流114,214从再生室104,204进料到反应室102,202。
反应室102,202和再生室104,204可以具有本领域已知的各种设计。在某些实施方案中,室102,104,202,204可以是固定床塞流反应器。在某些实施方案中,室102,104,202,204可以是流化床或提升管型反应器。在某些实施方案中,所述系统100,200可包括提升管柱。
在示例性实施方案中,制备合成气的方法可包括提供如上所述的包括反应室102,202和再生室104,204的系统100,200。反应室102,202可以包括氧化镍。甲烷和二氧化碳可以通过料流106,206进料至反应室102,202。进料至反应室102,202的甲烷和二氧化碳可以是干燥的(即不含或基本上不含水)。该方法可以是连续方法。换句话说,系统100,200可以连续操作。
在某些实施方案中,进料到反应室102,202中的甲烷与二氧化碳的比例(CH4:CO2)可以在约2:1至约1:2摩尔比之间。在某些实施方案中,进料到反应室102,202中的甲烷与二氧化碳的比例(CH4:CO2)可以为约2:1。甲烷与二氧化碳比例的变化可影响由系统100,200形成的合成气的组成。
甲烷和二氧化碳可以与反应室102,202内的氧化镍催化剂接触,以提供合成气(一氧化碳和氢气)以及水。由此制备的合成气可以通过产物流108,208从反应室102,202除去。也可以通过流108,208除去水。
在某些实施方案中,通过产物流108,208除去的合成气可以具有约1.5:1至约3:1(例如约2:1)的氢气:一氧化碳(H2:CO)比。
在某些实施方案中,水可以与产物流108,208中的合成气分离。水可以通过本领域已知的方法分离。作为非限制性实例,水可以通过冷凝分离,例如通过冷却产物流108,208。
在反应步骤中,如化学方程式(4)所示,氧化镍可以还原成还原的镍物质。还原的镍物质可能作为将甲烷和二氧化碳转化为合成气的催化剂无效。还原的镍物质的至少一部分可以通过料流110,210从反应室102,202移除到再生室104,204。在某些实施方案中,通过料流110,210从反应室102,202向再生室104,204移除的镍物质颗粒可以完全还原成金属镍,金属镍可以被涂覆在焦炭颗粒中。空气可以通过料流112,212送入再生室104,204。因此,空气可以与还原的镍物质接触以使还原的镍物质燃烧(氧化)。还原镍物质上的任何焦炭残余物也可以被氧化。因此,在再生室104,204内空气与还原的镍物质的接触可以在再生步骤中提供再生的氧化镍和热量,如化学方程式(5)所示。再生步骤也可以产生二氧化碳,如化学方程式(5)所示。
从再生步骤产生的再生氧化镍和热量的至少一部分然后可以通过料流114,214从再生室104,204被移除到反应室102,202。在某些实施方案中,通过料流114,214从再生室104,204向反应室102,202移除的镍物质颗粒可被完全氧化成再生的氧化镍。可以从再生室104,204中除去二氧化碳料流116,216。在某些实施方案中,至少一部分二氧化碳可通过料流218从再生室204移除至反应室202。
在某些实施方案中,系统100,200可以以类似于流化催化裂化(FCC)系统的模式操作。例如,甲烷和二氧化碳的一种或多种进料(例如料流106,206)可用于驱动镍物质(例如氧化镍和/或还原的镍物质)的颗粒通过反应室102,202并通过料流110,210进入再生室104,204。一个或多个氧气进料(例如空气料流112,212)可以保持镍物质的颗粒流化。镍物质(例如还原的镍物质)的颗粒可以在再生室104,204中再生(例如以提供再生的氧化镍),然后被移除到反应室102,202(例如通过料流114,214)。
在某些实施方案中,反应室102,202中的温度可以在约650℃至约1050℃之间,例如约650℃、约700℃、约750℃、约800℃、约850℃、约900℃、约950℃、约1000℃或约1050℃。反应室102,202中的温度可以在约750℃至约850℃之间。
在某些实施方案中,再生室104,204中的温度可以在约450℃至约850℃之间,例如约450℃、约500℃、约550℃、约600℃、约650℃、约700℃、约750℃、约800℃或约850℃。再生室104,204中的温度可以在约550℃至约750℃之间。
各种镍物质(镍氧化物(包括再生的镍氧化物)和还原的镍物质)可以在反应室102,202和再生室104,204之间循环。镍物质可以保持固体并且可以作为固体颗粒循环。镍物质可以在反应室102,202和再生室104,204内的温度下保持稳定,例如高达约850℃、约900℃、约950℃、约1000℃、约1050℃或高于1050℃。
系统100,200可以根据期望的合成气生产规模进行缩放。作为非限制性实例,实验室规模的系统100,200可包括直径约15mm至约20mm的反应和再生室102,202,104,204。在这样的实施方案中,通过系统100,200循环的镍物质颗粒的量可以在约70mL至约200mL之间,例如约100mL。
在某些实施方案中,系统100,200的气时空速(GHSV)可以在约3600h-1和约8000h-1之间,例如约5000h-1。在某些实施方案中,系统100,200内的压力可以是近似大气压(例如,约1巴)。
在某些实施方案中,通过反应室102,202和再生室104,204的气体的线性空速可以具有在约4m/s至约6m/s之间的线性空速。在某些实施方案中,可以调节气体通过室102,202,104,204的线性空度,以促进催化剂颗粒通过系统100,200(例如通过料流110,210,114,214)的循环。
当热量通过料流114,214从再生室104,204移除到反应室102,202时,由再生步骤产生的热量可被施加至反应步骤。以这种方式,放热的再生步骤可以用于驱动吸热反应步骤,减少了将外部来源的热施用到反应室102,202的需要。因此,从再生室104,204向反应室102,202移除热量可以降低能量消耗并改善过程的总体经济性。在某些实施方案中,热量和催化剂可以通过相同的料流114,214循环。
当通过料流218将二氧化碳从再生室204移除出到反应室202时,二氧化碳可以通过系统再循环并与甲烷反应以提供合成气。以这种方式,可以减少二氧化碳通过料流206的输入,从而改善过程的整体经济性。
如上所述,本申请公开的主题的方法和系统可以相对于将甲烷转化为合成气的某些现有方法具有某些优点。因为本申请公开的系统和方法可以使用空气而不是纯氧作为氧化剂,所以可以避免使用昂贵的氧气,从而改善经济性。在本申请公开的方法过程中产生的二氧化碳可以再循环到合成气制备反应中,这可以减少对外部二氧化碳源的需要并进一步改善经济性。本申请公开的主题的再生步骤可以向反应步骤提供热量,这可以降低能量消耗并且可以再次改善经济性。镍催化剂可以通过本申请公开的主题的系统循环,原位再生催化剂,并且不需要单独的催化剂再生步骤,这可以进一步提高经济性和效率。
实施例
实施例1.合成气的制备。
使用固定床反应器,使用分离的交替循环的反应和催化剂(氧化镍)再生制备合成气。向固定床反应器中加入8mL镧(La)和锰(Mn)混合氧化物催化剂。将CH4:CO2比为2:1(摩尔:摩尔)的甲烷和二氧化碳进料到反应器中。反应器温度为850℃。接触时间为1秒。甲烷和二氧化碳混合物的流速为480mL/分钟。
将合成气从反应器中移除。甲烷的转化率为80%,二氧化碳的转化率为85%。
然后用空气代替甲烷和二氧化碳的进料。以这种方式,将反应器从反应模式切换到再生模式。从反应器中移除二氧化碳,表明焦炭颗粒在催化剂上的燃烧。首先将空气送入反应器后十(10)分钟,二氧化碳形成显著下降,表明催化剂上焦炭碎片的充分燃烧和催化剂的再生。空气进入反应器共20分钟。然后用甲烷和二氧化碳的进料代替空气进料,完成反应循环。
虽然已经详细描述了本申请公开的主题及其优点,但是应当理解,在不脱离由所附权利要求书限定的所公开主题的精神和范围的情况下,可以在本文中进行各种改变、替换和变更。此外,所公开的主题的范围不旨在限于说明书中描述的特定实施方案。因此,所附权利要求书旨在在其范围内包括这样的替代方案。
Claims (13)
1.制备合成气的方法,包括:
a.提供反应室和再生室,其中所述反应室包含氧化镍;
b.将甲烷和二氧化碳进料到反应室中,从而使甲烷和二氧化碳与氧化镍接触以提供合成气和还原的镍物质;
c.将还原的镍物质从反应室移除至再生室;
d.将空气进料到再生室,从而使空气与还原的镍物质接触以提供再生的氧化镍和热量;和
e.将再生的氧化镍和热量从再生室移除至反应室。
2.根据权利要求1所述的方法,其中所述氧化镍包括固体载体。
3.根据权利要求1所述的方法,其中所述固体载体包括选自氧化铝、氧化镁和氧化硅的氧化物。
4.根据权利要求1所述的方法,其中所述氧化镍包括直径在约200μm至约400μm之间的颗粒。
5.根据权利要求1所述的方法,其中所述氧化镍包括助催化剂。
6.根据权利要求5所述的方法,其中所述助催化剂包括选自氧化镧(III)、氧化铈(III)、氧化铂(II)、氧化钡、氧化钙和氧化钾的氧化物。
7.根据权利要求1所述的方法,其中反应室中的温度在约650℃至约1050℃之间。
8.根据权利要求7所述的方法,其中反应室中的温度在约750℃至约850℃之间。
9.根据权利要求1所述的方法,其中再生室中的温度在约450℃至约850℃之间。
10.根据权利要求9所述的方法,其中再生室中的温度在约550℃至约750℃之间。
11.根据权利要求1所述的方法,还包括将二氧化碳从再生室移除到反应室。
12.一种用于将甲烷转化为合成气的系统,包括:
a.反应室,其含有还原的镍物质;
b.再生室,其含有再生的氧化镍;和
c.循环系统,其被配置为将还原的镍物质从反应室进料到再生室,并将再生的氧化镍从再生室进料到反应室。
13.根据权利要求12所述的系统,进一步包含提升管柱。
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CN111770793A (zh) * | 2018-05-29 | 2020-10-13 | 积水化学工业株式会社 | 催化剂、二氧化碳还原方法以及二氧化碳还原装置 |
CN112449615A (zh) * | 2018-08-03 | 2021-03-05 | 株式会社新生能源研究 | 水蒸气重整催化剂 |
CN112867557A (zh) * | 2018-09-18 | 2021-05-28 | 苏黎世联邦理工学院 | 用于生产合成气的方法 |
CN115090291A (zh) * | 2022-05-24 | 2022-09-23 | 天津大学 | 一种耦合钙循环二氧化碳捕集和甲烷干重整制合成气的催化剂制备方法及应用 |
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CN110479288B (zh) * | 2019-08-22 | 2020-12-11 | 西南化工研究设计院有限公司 | 一种干气制氢转化催化剂及其制备方法 |
US11724937B2 (en) * | 2021-12-22 | 2023-08-15 | King Abdulaziz University | Method of dry reforming of methane |
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CN111770793A (zh) * | 2018-05-29 | 2020-10-13 | 积水化学工业株式会社 | 催化剂、二氧化碳还原方法以及二氧化碳还原装置 |
CN112449615A (zh) * | 2018-08-03 | 2021-03-05 | 株式会社新生能源研究 | 水蒸气重整催化剂 |
CN112867557A (zh) * | 2018-09-18 | 2021-05-28 | 苏黎世联邦理工学院 | 用于生产合成气的方法 |
CN112867557B (zh) * | 2018-09-18 | 2023-11-07 | 苏黎世联邦理工学院 | 用于生产合成气的方法 |
CN115090291A (zh) * | 2022-05-24 | 2022-09-23 | 天津大学 | 一种耦合钙循环二氧化碳捕集和甲烷干重整制合成气的催化剂制备方法及应用 |
CN115090291B (zh) * | 2022-05-24 | 2024-01-09 | 天津大学 | 一种耦合钙循环二氧化碳捕集和甲烷干重整制合成气的催化剂制备方法及应用 |
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