静电纺丝法制备高活性多孔Ni/SiO2甲烷化催化剂

doi:10.11949/0438-1157.20200251

摘要/Abstract

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

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

中图分类号:

TQ 546.4

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.

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.

图/表 11

图1 Ni/SiO2催化剂SEM图

Fig.1 SEM images of Ni/SiO2 catalysts

表1 Ni/SiO2催化剂物理性质

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)

图2 Ni/SiO2催化剂的N2吸脱附等温曲线和孔径分布

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

图3 Ni/SiO2催化剂XRD谱图

Fig.3 XRD patterns of Ni/SiO2 catalysts

图4 煅烧后和还原后Ni/SiO2催化剂TEM图和粒径分布

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

图5 Ni/SiO2催化剂H2-TPR曲线

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

图6 Ni/SiO2催化剂催化活性

Fig.6 Catalytic performance of Ni/SiO2 catalysts

图7 Ni/P-SiO2-ES和Ni/SiO2-ES催化剂稳定性

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

表2 Ni/P-SiO2-ES和Ni/SiO2-ES催化剂稳定性测试

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

图8 100 h反应后Ni/SiO2催化剂TEM图和粒径分布

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

图9 100 h反应前后Ni/SiO2催化剂TGA曲线

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

参考文献 31

1	周芳, 姜波. 煤制天然气工艺流程优化探讨[J]. 化工设计, 2016, 26(3): 7-10.
	Zhou F, Jiang B. Discussion on coal-to-natural gas process flow optimization[J]. Chemical Engineering Design, 2016, 26(3): 7-10.
2	Roensch S, Schneider J, Matthischke S, et al. Review on methanation — from fundamentals to current projects[J]. Fuel, 2016, 166: 276-296.
3	胡大成, 高加俭, 贾春苗, 等. 甲烷化催化剂及反应机理的研究进展[J]. 过程工程学报, 2011, 11(5): 880-893.
	Hu D C, Gao J J, Jia C M, et al. Research advances in methanation catalysts and their catalytic mechanisms[J]. The Chinese Journal of Process Engineering, 2011, 11(5): 880-893.
4	Bai X B, Wang S, Sun T J, et al. The sintering of Ni/Al₂O₃ methanation catalyst for substitute natural gas production[J]. Reaction Kinetics Mechanisms and Catalysis, 2014, 112(2): 437-451.
5	Bartholomew C H. Mechanisms of catalyst deactivation[J]. Applied Catalysis A: General, 2001, 212(1/2): 17-60.
6	Enger B C, Holmen A. Nickel and Fischer-Tropsch synthesis[J]. Catalysis Reviews-Science and Engineering, 2012, 54(4): 437-488.
7	Klaigaew K, Samart C, Chaiya C, et al. Effect of preparation methods on activation of cobalt catalyst supported on silica fiber for Fischer-Tropsch synthesis[J]. Chemical Engineering Journal, 2015, 278: 166-173.
8	Mhadmhan S, Natewong P, Prasongthum N, et al. Investigation of Ni/SiO₂ fiber catalysts prepared by different methods on hydrogen production from ethanol steam reforming[J]. Catalysts, 2018, 8(8): 1-18.
9	Ren J, Li H D, Jin Y Y, et al. Silica/titania composite-supported Ni catalysts for CO methanation: effects of Ti species on the activity, anti-sintering, and anti-coking properties[J]. Applied Catalysis B: Environmental, 2017, 201: 561-572.
10	Jin G J, Gu F N, Liu Q, et al. Highly stable Ni/SiC catalyst modified by Al₂O₃ for CO methanation reaction[J]. RSC Advances, 2016, 6(12): 9631-9639.
11	张加赢, 辛忠, 孟鑫, 等. 基于MCM-41的镍基甲烷化催化剂活性与稳定性[J]. 化工学报, 2014, 65(1): 160-168.
	Zhang J Y, Xin Z, Meng X, et al. Activity and stability of nickel based MCM-41 methanation catalysts for production of synthetic natural gas[J]. CIESC Journal, 2014, 65(1): 160-168.
12	Tao M, Meng X, Xin Z, et al. Synthesis and characterization of well dispersed nickel-incorporated SBA-15 and its high activity in syngas methanation reaction[J]. Applied Catalysis A: General, 2016, 516: 127-134.
13	Cheng C B, Shen D K, Xiao R, et al. Methanation of syngas (H₂/CO) over the different Ni-based catalysts[J]. Fuel, 2017, 189: 419-427.
14	Zeng Y, Ma H F, Zhang H T, et al. Highly efficient NiAl₂O₄-free Ni/γ-Al₂O₃ catalysts prepared by solution combustion method for CO methanation[J]. Fuel, 2014, 137: 155-163.
15	Xue J J, Xie J W, Liu W Y, et al. Electrospun nanofibers: new concepts, materials, and applications[J]. Accounts of Chemical Research, 2017, 50(8): 1976-1987.
16	刘力菲, 李伟, 黄潇楠. 静电纺丝纳米纤维的制备与应用[J]. 首都师范大学学报(自然科学版), 2017, 38(1): 58-63.
	Liu L F, Li W, Huang X N. Preparation and application of the electrospinning nanofibers[J]. Journal of Capital Normal University (Natural Science Edition), 2017, 38(1): 58-63.
17	Zou R, Wen S P, Zhang L Q, et al. Preparation of Rh-SiO₂ fiber catalyst with superior activity and reusability by electrospinning[J]. RSC Advances, 2015, 5(121): 99884-99891.
18	Li W H, Zhang A F, Jiang X, et al. The anti-sintering catalysts: Fe-Co-Zr polymetallic fibers for CO₂ hydrogenation to C₂ = -C₄ = -rich hydrocarbons[J]. Journal of CO₂ Utilization, 2018, 23: 219-225.
19	Zhao Y Y, Wang H Y, Lu X F, et al. Fabrication of refining mesoporous silica nanofibers via electrospinning[J]. Materials Letters, 2008, 62(1): 143-146.
20	Wang X Q, Dou L Y, Yang L, et al. Hierarchical structured MnO₂@SiO₂ nanofibrous membranes with superb flexibility and enhanced catalytic performance[J]. Journal of Hazardous Materials, 2017, 324: 203-212.
21	辛忠, 何璐铭, 孟鑫. 一种镍基纯硅型分子筛催化剂及其制备方法与应用: 202010147006.7[P]. 2020-03-05.
	Xin Z, He L M, Meng X. A nickel-based pure silicon molecular sieve catalyst and its preparation and application: 202010147006.7[P]. 2020-03-05.
22	Kang H G, Zhu Y H, Yang X L, et al. A novel catalyst based on electrospun silver-doped silica fibers with ribbon morphology[J]. Journal of Colloid and Interface Science, 2010, 341(2): 303-310.
23	Fang C, Zhang D S, Shi L Y, et al. Highly dispersed CeO₂ on carbon nanotubes for selective catalytic reduction of NO with NH₃[J]. Catalysis Science & Technology, 2013, 3(3): 803-811.
24	Guo X Z, Yang H, Cao M. Nucleation and crystallization behavior of Li₂O-Al₂O₃-SiO₂ system glass-ceramic containing little fluorine and no-fluorine[J]. Journal of Non-Crystalline Solids, 2005, 351(24/25/26): 2133-2137.
25	赵醒, 胡彦杰, 蒋洁超, 等. 过渡金属原位掺杂Pt/TiO₂的喷雾燃烧制备及其CO氧化性能[J]. 华东理工大学学报(自然科学版), 2018, 44(6): 823-830.
	Zhao X, Hu Y J, Jiang J C, et al. Transition metal in situ doping Pt/TiO₂ by flame spray pyrolysis for CO oxidation[J]. Journal of East China University of Science and Technology (Natural Science Edition), 2018, 44(6): 823-830.
26	Zhao B R, Chen Z P, Chen Y J, et al. Syngas methanation over Ni/SiO₂ catalyst prepared by ammonia-assisted impregnation[J]. International Journal of Hydrogen Energy, 2017, 42(44): 27073-27083.
27	Gao J J, Wang Y L, Ping Y, et al. A thermodynamic analysis of methanation reactions of carbon oxides for the production of synthetic natural gas[J]. RSC Advances, 2012, 2(6): 2358-2368.
28	Borodko Y, Somorjai G A. Catalytic hydrogenation of carbon oxides — a 10-year perspective[J]. Applied Catalysis A: General, 1999, 186(1/2): 355-362.
29	Tao M, Xin Z, Meng X, et al. Highly dispersed nickel within mesochannels of SBA-15 for CO methanation with enhanced activity and excellent thermostability[J]. Fuel, 2017, 188: 267-276.
30	Shinde V M, Madras G. CO methanation toward the production of synthetic natural gas over highly active Ni/TiO₂ catalyst[J]. AIChE Journal, 2014, 60(3): 1027-1035.
31	Liu S S, Jin Y Y, Han Y, et al. Highly stable and coking resistant Ce promoted Ni/SiC catalyst towards high temperature CO methanation[J]. Fuel Processing Technology, 2018, 177: 266-274.

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静电纺丝法制备高活性多孔Ni/SiO₂甲烷化催化剂

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

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