Preparation of highly dispersed silicon spheres supported cobalt-based catalysts and their catalytic performance for Fischer-Tropsch synthesis
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摘要: 利用等体积浸渍法将钴前驱体浸渍在结构规整的硅球(SP)载体上,在不同强度的等离子体场中分解钴盐,制备出一系列高分散Co/SP催化剂。采用X射线粉末衍射、氮气物理吸附-脱附、扫描透射电子显微镜和傅里叶红外变换光谱等表征手段对催化剂结构进行表征,并在固定反应器上进行费-托合成催化性能测试,探讨等离子体处理强度对费-托合成催化剂的分散度、还原度、相互作用的影响规律。结果表明,等离子体处理催化剂在费-托合成反应中表现出比焙烧样品更优越的催化性能,其中,Co/SP-P650W由于具有较适宜的分散度和相对较高的还原性,呈现出最高的费-托合成反应活性。Abstract: A series of silicon spheres supported cobalt catalysts were prepared by incipient wetness impregnation followed by decomposition under treatment of glow discharge plasma with different intensities. The catalysts were characterized by X-ray powder diffraction, N2 physical adsorption-desorption, H2 temperature-programmed reduction, transmission electron microscope and Fourier-Transform Infrared spectroscopy. The Fischer-Tropsch synthesis performance were tested on a fixed bed reactor. The influence of plasma treatment on cobalt dispersion, reducibility and cobalt-support interaction were analyzed and discussed. The results showed that the plasma-treated catalysts had better catalytic performance than the calcined sample. The Co/SP-P650W catalyst showed the highest reaction activity due to the proper cobalt dispersion and higher cobalt reducibility.
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表 1 Co/SP催化剂等离子体处理参数
Table 1 Plasma treatment parameters of Co/SP catalysts
Catalyst Output power/W Duty factor/% Glow discharge voltage/Pa Treatment time/h Temperature of the treating chamber/℃ Treatment atmosphere Co/SP-P430W 430 20 100 1 80 air Co/SP-P650W 650 20 100 1 142 air Co/SP-P1900W 1900 20 100 1 203 air 表 2 还原前后Co/SP催化剂的钴颗粒尺寸(XRD和TEM)
Table 2 Cobalt particle sizes of Co/SP catalysts before and after reduction (XRD and TEM)
Catalyst ${D_{{\rm{C}}{{\rm{o}}_{\rm{3}}}{{\rm{O}}_{\rm{4}}}}} $/(TEM, nm) ${D_{{\rm{C}}{{\rm{o}}_{\rm{3}}}{{\rm{O}}_{\rm{4}}}}} $/(XRD, nm) DCoO-red/(XRD, nm) DCoO-red/(TEM, nm) Co/SP-C − 21.6 21.3(Co) − Co/SP-P430W 3.1 4.6 6.3 − Co/SP-P650W 6.4 6.2 6.0 7.7 Co/SP-P1900W 7.4 7.5 7.9 − 表 3 还原前后Co/SP催化剂的Co 2p3/2 XPS结合能和表面元素比值
Table 3 Co 2p3/2 binding energy and surface element ratio of Co/SP catalysts before and after reduction
Catalyst Co 2p3/2 E/eV Co 2p3/2-red E/eV Co/Si Co/Si-red Co/SP-C 780.4 781.7 0.012 0.041 Co/SP-P430W 781.1 782.0 0.075 0.064 Co/SP-P650W 781.2 781.8 0.057 0.067 Co/SP-P1900W 781.6 781.9 0.037 0.054 表 4 Co/SP催化剂的费-托合成反应性能
Table 4 FTs performance of Co/SP catalysts
Catalyst CO conversion/% CO2 selectivity/% Hydrocarbon selectivity/% CH4 C2−C4 C5 + Co/SP-C 6.5 0.4 6.9 7.4 85.7 Co/SP-P430W 25.2 0.4 9.9 10.1 80.0 Co/SP-P650W 37.3 1.4 6.4 7.8 85.8 Co/SP-P1900W 29.6 0.2 6.1 8.8 85.1 -
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