Production of hydrogen and carbon nanofibers by methane decomposition over the Ni/SiO2 catalyst
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摘要: 甲烷催化裂解制氢具有过程简单、产物易分离、无COx产生等优点，是一种潜在的制氢工艺。本工作采用浸渍法制备Ni/SiO2介孔催化剂，通过N2吸附-脱附、X射线衍射、程序升温还原、扫描电子显微镜和透射电子显微镜对反应前后的催化剂结构及生成炭的形貌进行表征，研究了焙烧温度、金属负载量和反应温度对其甲烷催化裂解性能的影响。结果表明，所制备的Ni/SiO2催化剂具有较好的介孔结构，焙烧温度对催化剂的结构性质和催化性能影响较小，但会改变Ni晶粒在催化剂表面团聚程度。随着金属负载量的增加，催化剂的活性呈现先增加后降低的趋势，其中30% Ni/SiO2催化剂的催化活性最佳。反应温度会显著影响催化剂的活性、稳定性以及生成炭的形态；较高反应温度导致催化剂的稳定性降低和包覆炭的形成。在30% Ni/SiO2催化剂上、550 °C下反应1000 min，甲烷转化率为9.8%，纤维炭产率约为650 °C下的7.2倍。Abstract: Catalytic decomposition of methane is a promising route for hydrogen production owing to simple operation, easy separation of the products and no COx emission. In this work, a mesoporous Ni/SiO2 catalyst was prepared by impregnation method and used in methane decomposition; the fresh and spent catalysts and the morphology of deposited carbon were characterized by N2 adsorption-desorption, X-ray diffraction, hydrogen temperature programmed reduction, scanning electron microscopy and transmission electron microscopy. The effects of calcination temperature, metal loading and reaction temperature on the catalytic performance of Ni/SiO2 in methane decomposition were investigated. The results show that the Ni/SiO2 catalyst exhibits mesoporous structure. The calcination temperature has a slight effect on the textural properties and catalytic performances of Ni/SiO2, but a significant influence on the agglomeration degree of Ni particles on the catalyst surface. The catalytic activity of Ni/SiO2 increases first with increasing the metal loading up to 30% and then declines with a further increase of metal loading. Meanwhile, the reaction temperature has a remarkable influence on the catalytic activity and stability and the state of the deposited carbon; a high temperature results in the decrease of the catalytic stability and the formation of encapsulated carbon. In particular, for the methane decomposition over the 30% Ni/SiO2 catalyst, the methane conversion of about 9.8% was obtained at 500 °C after reaction for 1000 min; the yield of carbon nanofiber at 500 °C is about 7.2 times higher than that at 650 °C.
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Key words:
- methane decomposition /
- Ni/SiO2 /
- hydrogen /
- carbon nanofiber
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图 2 不同焙烧温度制备催化剂的N2吸附-脱附曲线(a)、孔径分布(b)和甲烷转化率(c)
Figure 2 N2 adsorption/desorption isotherms (a), pore size distribution (b) and methane conversion (c) of the catalysts prepared under different calcination temperatures
图 3 不同焙烧温度制备的催化剂H2-TPR谱图(a)和反应前后的XRD谱图(b)
Figure 3 H2-TPR profiles (a) and XRD patterns (b) of the catalysts prepared under different calcination temperatures
图 4 不同焙烧温度所制备催化剂反应后的SEM和TEM照片
Figure 4 SEM ((a)–(f)) and TEM ((g) and (h)) images of the catalysts prepared under different calcination temperatures after reaction
(a): 400 °C; (b): 450 °C; (c): 500 °C; (d): 550 °C; (e): 600 °C; (f): 650 °C; (g): 400 °C; (h): 650 °C
图 5 不同镍负载量所制备催化剂的N2吸附-脱附曲线(a)、孔径分布(b)和甲烷转化率(c)
Figure 5 N2 adsorption/desorption isotherms (a), pore size distribution(b) and methane conversion(c) of the catalysts prepared under different Ni contents
图 6 不同镍负载量所制备催化剂甲烷裂解反应前后的XRD谱图
Figure 6 XRD patterns of the catalysts prepared under different Ni contents
图 7 不同镍负载量所制备催化剂反应后的SEM和TEM照片
Figure 7 SEM ((a)–(d)) and TEM ((e)–(h)) images of the catalysts prepared under different Ni contents after reaction
((a), (e): 10% Ni/SiO2; (b), (f): 20% Ni/SiO2 (c); (g): 30% Ni/SiO2; (d), (h): 40% Ni/SiO2)
图 8 不同反应温度下催化剂的甲烷转化率(a)以及反应前后催化剂的XRD谱图(b)
Figure 8 Methane conversion (a) and XRD patterns (b) of the spent catalysts after reaction under different temperatures
图 9 不同裂解温度反应后催化剂的SEM照片
Figure 9 SEM images of the spent catalysts after reaction under different temperatures
(a): 550 ℃; (b): 600 ℃; (c): 650 ℃
表 1 不同焙烧温度制备催化剂的结构性质
Table 1 Textural properties of the catalysts prepared under different calcination temperatures
Sample SBET/（m2·g−1） vt/（cm3·g−1） dave/ nm SiO2 196.3 0.60 12.5 Ni/SiO2-400 170.2 0.88 16.9 Ni/SiO2-450 170.4 0.87 17.2 Ni/SiO2-500 160.4 0.85 17.1 Ni/SiO2-550 166.3 0.90 17.1 Ni/SiO2-600 162.7 0.90 15.4 Ni/SiO2-650 162.5 0.95 18.1 
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表 2 不同焙烧温度所制备催化剂反应前后镍颗粒平均粒径
Table 2 Average particle size of nickel particles before and after reaction of catalyst prepared under different calcination temperatures
Sample Particle size d/nm 400 ℃ 450 ℃ 500 ℃ 550 ℃ 600 ℃ 650 ℃ Fresh 16.9 17.8 18.8 18.9 19.2 19.6 Spent 17.0 18.2 18.9 19.1 19.9 20.9
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表 3 不同镍负载量所制备催化剂的结构性质
Table 3 Textural properties of the catalysts prepared under different Ni contents
Sample SBET/ (m2·g−1) vt/ (cm3·g−1) dave/ nm 10% Ni/SiO2 170.2 0.88 16.9 20% Ni/SiO2 161.8 0.78 15.9 30% Ni/SiO2 149.7 0.73 17.5 40% Ni/SiO2 128.8 0.48 13.5
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表 4 不同负载量所制备催化剂反应前后镍颗粒平均粒径
Table 4 Average particle size of nickel particles before and after reaction of catalyst prepared under different Ni contents
Sample Particle size d/nm 10% 20% 30% 40% Fresh 16.9 21.5 23.7 25.0 Spent 17.0 22.9 24.5 27.6
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