Highly coke-resistant ordered mesoporous Ni/SiC with large surface areas in CO2 reforming of CH4
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摘要: 采用纳米浇铸法制备了高比表面积（345 m2/g）且孔径均一的有序介孔SiC材料（SiC-OM），以商用SiC（49 m2/g，SiC-C）材料为参比载体。采用等体积浸渍法分别制备了Ni/SiC-OM和Ni/SiC-C，并考察其在CH4-CO2重整反应中的催化性能。利用ICP、BET、XRD、H2-TPR、XPS、HRTEM、TG和Raman等手段对反应前后的两种催化剂进行表征。结果表明，在700℃、1.013×105 Pa和12 L/（h·g）的重整条件下，Ni/SiC-OM的平均积炭速率比Ni/SiC-C降低了一个数量级，这主要归因于强金属-载体相互作用和有序介孔骨架的"限域效应"作用。Abstract: An ordered mesoporous SiC (SiC-OM) material with high specific surface area (345 m2/g) and narrow pore distribution was prepared by a nanocasting method, and a commercial SiC (49 m2/g, SiC-C) was used as a reference carrier. The Ni/SiC-C and Ni/SiC-OM catalysts were prepared by an incipient wetness impregnation method, and tested in the CO2 reforming of CH4(CRM). The textural properties of fresh and used catalysts were characterized by means of ICP, BET, XRD, H2-TPR, XPS, HRTEM, TG, and Raman. The results suggested the average carbon deposition rate over the Ni/SiC-OM decreased one order of magnitude compared with the Ni/SiC-C during 50 h of CRM reaction, due to the strong interaction between Ni species and SiC-OM support and confinement effect of rigid mesoporous skeleton.
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Key words:
- methane /
- dry reforming /
- ordered mesopores /
- SiC /
- carbon deposition
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图 1 Ni/SiC-C (a)和Ni/SiC-OM (b)催化剂的催化性能
Figure 1 Catalytic performances of the Ni/SiC-C (a) and Ni/SiC-OM (b) catalysts
(reaction condition: 700 ℃, 1.013×105 Pa, CH4:CO2=1 and GHSV=12 L/(h·g))
图 2 Ni-Y/SiC-C (a)和Ni-Y/SiC-OM (b)催化剂的催化性能
Figure 2 Catalytic performances of the Ni-Y/SiC-C (a) and Ni-Y/SiC-OM (b) catalysts
(reaction condition: 700 ℃, 1.013×105 Pa, CH4:CO2 = 1 and GHSV = 12 L/(h·g))
图 3 载体、新鲜催化剂和反应后催化剂的XRD谱图
Figure 3 XRD patterns of the samples
(●: β-SiC; ◆: Ni; ▲: NiO; ■: graphite carbon)
图 4 SiC-OM基材料的N2吸附-脱附曲线(a)和孔径分布(b)
Figure 4 N2 adsorption-desorption isotherms (a) and pore size distributions (b) of the SiC-OM-derived samples
图 7 新鲜催化剂的Ni 2p3/2 (a)和Si 2p (b) XPS谱图
Figure 7 Ni 2p3/2 (a) and Si 2p (b) XPS patterns of the fresh catalysts
图 8 SiC-C (a)、新鲜Ni/SiC-C (b)、反应后Ni/SiC-C (c)、SiC-OM (d)、新鲜Ni/SiC-OM (e)和反应后Ni/SiC-OM (f)的TEM照片
Figure 8 TEM images of the SiC-C (a), fresh Ni/SiC-C (b), used Ni/SiC-C (c), SiC-OM (d), fresh Ni/SiC-OM (e), and used Ni/SiC-OM (f) catalysts
图 9 反应后催化剂的TG曲线(a)和Raman谱图(b)
Figure 9 TG curves (a) and Raman profiles (b) of the used catalysts
表 1 催化剂的结构性质
Table 1 Structural properties of the samples
Sample Ni content w/% BET surface A/(m2·g-1) Pore volume v/(cm3·g-1) Average pore diameter d/nm SiC-C - 49 0.15 13.4 Fresh Ni/SiC-C 9.4 44 0.13 15.0 Used Ni/SiC-C - 49 0.21 17.4 SiC-OM - 345 0.31 4.3 Fresh Ni/SiC-OM 7.9 300 0.27 5.3 Used Ni/SiC-OM - 231 0.25 5.8 
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