用传统湿式浸渍法制备La2O3掺杂的商业γ-Al2O3负载的沼气重整催化剂Ni-Co/La2O3-γ-Al2O3,通过对NiCo双金属催化剂上沼气重整制氢在常压下的宏观动力学分析,得出该催化剂上CH4与CO2消耗、H2与CO生成时的表观反应速率方程。通过改变进料中CH4与CO2的分压,求出各物质的反应分级数,确定总反应为拟一级反应。通过改变反应温度并利用Arrhenius方程求解出各物质的表观活化能与指前因子,从而推导出常压下反应温度为500~900 ℃时,CH4与CO2的表观消耗速率方程以及H2与CO的表观生成速率方程。
Abstract
Ni-Co bimetallic catalysts（Ni-Co/La2O3-γ-Al2O3） supported by commercial γ-Al2O3 modified with La2O3 were prepared by conventional incipient wetness impregnation for biogas reforming. A macro-kinetic study on biogas reforming in Ni-Co bimetallic catalyst has been investigated. The apparent reaction rate equations of CH4 and CO2 consumption and H2 and CO production were suggested. The partial orders of reaction of CH4 and CO2 consumption and H2 and CO production were solved by changing partial pressures of CH4 and CO2 in feed. The total reaction order is pseudo first-order. Apparent activation energy and preexponential factor of the catalysts were also calculated by varying the reaction temperature. The apparent reaction rate equations of CH4 and CO2 consumption and H2 and CO production were deduced at the temperature from 500 to 900 ℃ in the normal atmospheric pressure.
关键词
镍 /
钴 /
双金属催化剂 /
沼气重整 /
制氢 /
宏观动力学
Key words
nickel /
cobalt /
bimetallic catalyst /
biogas reforming /
hydrogen production /
macrokinetics
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参考文献
[1] OEMAR U, KATHIRASER Y, MO L, et al.CO2 reforming of methane over highly active La-promoted Ni supported on SBA-15 catalysts mechanism and kinetic modeling[J]. Catalysis science & technology, 2016, 6(4): 1173-1186.
[2] AZZAM M, ARAMOUNI N A K, AHMAD M N, et al. Dynamic optimization of dry reformer under catalyst sintering using neural networks[J]. Energy conversion and management, 2018, 157: 14-156.
[3] TSIPOURIARI V A, VERYKIOS X E.Kinetic study of the catalytic reforming of methane with carbon dioxide to synthesis gas over Ni/La2O3 catalyst[J]. Catalysis today, 2001, 64(1-2): 83-90.
[4] NANDINII A, PANT K K, DHINGRA S C.Kinetic study of the catalytic carbon dioxide reforming of methane to synthesis gas over Ni-K/CeO2-Al2O3 catalyst[J]. Applied catalysis A: general, 2006, 308: 119-127.
[5] WEI J M, IGLESIA E.Isotopic and kinetic assessment of the mechanism of reactions of CH4 with CO2 or H2O to form synthesis gas and carbon on nickel catalysts[J]. Journal of catalysis, 2004, 224(2): 370-383.
[6] KARAM L, HASSAN N E.Advantages of mesoporous silica based catalysts in methane reforming by CO2 from kinetic perspective[J]. Environmental chemical engineering, 2018, 6(4): 4289-4297.
[7] AYODELE B V, ABDULLAH S B, CHENG C K.Kinetics and mechanistic studies of CO-rich hydrogen production by CH4/CO2 reforming over Praseodymia supported cobalt catalysts[J]. International journal of hydrogen energy, 2017, 42(47): 28408-28424.
[8] DELGADO K H, MAIER L, TISCHER S, et al.Surface reaction kinetics of steam-and CO2-reforming as well as oxidation of methane over nickel-based catalysts[J]. Catalysts, 2015, 5(2): 871-904.
[9] ZAMBRANO D, SOLER J, HERGUIDO J, et al.Kinetic study of dry reforming of methane over Ni-Ce/Al2O3 catalyst with deactivation[J]. Topics in catalysis, 2019, 62(5-6): 456-466.
[10] KHOJA A H, TAHIR M, AMIN N A S, et al. Kinetic study of dry reforming of methane using hybrid DBD plasma reactor over La2O3 co-supported Ni/MgAl2O4 catalyst[J]. International journal of hydrogen energy, 2020, 45(22): 12256-12271.
[11] XU J K, ZHOU W, LI Z J, et al.Biogas reforming for hydrogen production over nickel and cobalt bimetallic catalyst[J]. International journal of hydrogen energy, 2009, 34(16): 6646-6654.
[12] XU J K, ZHOU W, LI Z J, et al.Biogas reforming for hydrogen production over Ni-Co bimetallic catalyst: effect of operating conditions[J]. International journal of hydrogen energy, 2010, 35(23): 13013-13020.
[13] 徐军科, 沈利红, 周伟, 等. Ni-Co双金属催化剂上沼气重整制氢机理[J]. 物理化学学报, 2011, 27(43): 697-704.
XU J K, SHEN L H, ZHOU W, et al.Biogas reforming for hydrogen production over Ni-Co bimetallic catalyst: Mechanistic aspects[J]. Acta physico-chimica sinica, 2011, 27(43): 697-704.
[14] 赵健, 周伟, 徐军科, 等. 预处理方法对Ni-Co双金属催化剂性能与结构的影响[J]. 物理化学学报, 2013, 29(4): 806-812.
ZHAO J, ZHOU W, XU J K, et al.Effect of pretreatment routes on the performance and structure of Ni-Co bimetallic catalysts[J]. Acta physico-chimica sinica, 2013, 29(4): 806-812.
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