Highly efficient porous Ni/SiO2 catalysts prepared by electrospinning method for CO methanation

doi:10.11949/0438-1157.20200251

Abstract

Abstract:

Porous Ni/SiO₂ catalysts were prepared by electrospinning using P123 as template and the catalytic performance in CO methanation was evaluated. The synthesized catalyst was characterized by N₂ physisorption measurements, scanning electron microscopy (SEM), X-ray diffraction (XRD), hydrogen temperature-programmed reduction (H₂-TPR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The results showed that Ni particles were highly dispersed on the silica nanofibers. The presence of pore structure in electrospun fibers immensely increased the specific surface area. Moreover, the porous Ni/SiO₂ catalyst exhibited small particle size and strong metal-support interaction, which led to excellent catalytic activity with 96.4% CO conversion and 86.4% CH₄ selectivity at 450 °C under 0.1 MPa with a WHSV of 15000 ml/(g·h). The 100-hour lifetime test indicated that the porous Ni/SiO₂catalyst had excellent stability. This method provides a new idea for the industrial preparation of methanation catalysts with high catalytic activity and without secondary molding.

Key words: catalyst, preparation, silica, electrospinning, CO methanation

摘要：

以三嵌段共聚物P123为模板剂，采用静电纺丝法制备了多孔Ni/SiO₂催化剂，考察其在CO甲烷化中的催化性能。采用N₂物理吸脱附测试、扫描电子显微镜（SEM）、X射线衍射（XRD）、H₂-程序升温还原（H₂-TPR）、透射电子显微镜（TEM）、热重分析（TGA）对催化剂的结构性质进行表征。结果表明，静电纺丝法制备的多孔Ni/SiO₂催化剂活性组分Ni在SiO₂载体纤维上高度分散，比表面积大，Ni颗粒尺寸小，金属与载体相互作用强，在CO甲烷化反应中表现出优异的催化活性和稳定性。在温度450℃，压力0.1 MPa，质量空速15000 ml/（g·h）条件下，多孔Ni/SiO₂催化剂CO转化率最高可达96.4%，CH₄选择性可达86.4%。此方法为工业上制备高催化活性且无须二次成型的甲烷化催化剂提供了新思路。

关键词: 催化剂, 制备, 二氧化硅, 静电纺丝, CO甲烷化

CLC Number:

TQ 546.4

Luming HE,Zhong XIN,Wenli GAO,Jia GU,Xin MENG. Highly efficient porous Ni/SiO₂ catalysts prepared by electrospinning method for CO methanation[J]. CIESC Journal, 2020, 71(11): 5007-5015.

何璐铭,辛忠,高文莉,顾佳,孟鑫. 静电纺丝法制备高活性多孔Ni/SiO₂甲烷化催化剂[J]. 化工学报, 2020, 71(11): 5007-5015.

Figures/Tables 11

Fig.1 SEM images of Ni/SiO2 catalysts

Table 1 Physicochemical properties of Ni/SiO2 catalysts

催化剂

S_BET/

(m²/g)

V_pore/

(cm³/g)

D_pore/nm

D_Ni^①/nm

Ni^②/

%(mass)

Fig.2 Nitrogen adsorption-desorption isotherms and pore size distributions of Ni/SiO2 catalysts

Fig.3 XRD patterns of Ni/SiO2 catalysts

Fig.4 TEM images and particle size distribution of calcined and reduced Ni/SiO2 catalysts

Fig.5 H2-TPR profiles of Ni/SiO2 catalysts

Fig.6 Catalytic performance of Ni/SiO2 catalysts

Fig.7 Catalytic stability of Ni/P-SiO2-ES and Ni/SiO2-ES catalysts

Table 2 Catalytic stability of Ni/P-SiO2-ES and Ni/SiO2-ES catalysts

反应时间/h	Ni/P-SiO₂-ES		Ni/SiO₂-ES
反应时间/h	CO转化率/%	CH₄选择性/%	CO转化率/%	CH₄选择性/%
0	96.5	86.1	85.5	83.7
100	87.9	83.7	70.7	81.2

Fig.8 TEM images and particle size distribution of the spent Ni/SiO2 catalysts after 100 h stability test

Fig.9 TGA curves of Ni/SiO2 catalysts before and after 100 h stability test

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Highly efficient porous Ni/SiO₂ catalysts prepared by electrospinning method for CO methanation

静电纺丝法制备高活性多孔Ni/SiO₂甲烷化催化剂

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References 31

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