Influence of calcination temperature on the structure and catalytic reforming performance of Ni/CaO-Al2O3 catalyst
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摘要: 采用共沉淀法制备了一系列具有类水滑石结构前驱体的Ni/CaO-Al2O3复合催化剂，考察了制备过程中焙烧温度对复合催化剂结构及性能的影响。结果表明，焙烧温度可调控活性组分Ni与载体之间的相互作用力，进而调变复合催化剂的比表面积、活性组分Ni的颗粒粒径。当焙烧温度为700 ℃时，Ni与载体之间相互作用力适宜，复合催化剂具有最大的比表面积（21.42 m2/g）和最小的Ni颗粒粒径（19.51 nm）；该复合催化剂在CO2吸附强化CH4/H2O重整制氢过程中可得到98.31%的H2浓度和94.87%的CH4转化率，循环10次后，H2浓度仍能保持在97.35%以上。这是因为大的比表面积为反应提供了更多的活性位点，利于CO2吸附过程的强化，而小的Ni颗粒粒径提高了复合催化剂的抗烧结能力。Abstract: Considering the tunable structure of hydrotalcite-like compounds, co-precipitation method was employed to synthesize Ni/CaO-Al2O3 composite catalysts. The influence of calcination temperature on the structure and catalytic reforming performance of Ni/CaO-Al2O3 catalyst investigated. The results showed that the specific surface area and Ni particle size of the as-synthesized composite catalysts were greatly affected by calcination temperature of the precursor derived from the variable interaction between the Ni and the support. When the calcination temperature was 700 ℃, the composite catalyst obtained a specific surface area of 21.42 m2/g and Ni particle size of 19.51 nm. The catalytic evaluation showed that the composite catalyst possessed a H2 concentration of 98.31% and a CH4 conversion of 94.87%, and H2 concentration exceeded 97.35% even after 10 cyclic runs. The high catalytic activity was ascribed to the higher specific surface area, which provided more active sites and enhanced CO2 sorption. The smaller Ni particle size improved the anti-sintering capacity of the composite catalyst, endowing the composite catalyst superior stability.
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图 3 不同焙烧温度复合催化剂的XRD谱图
Figure 3 XRD patterns of the composite catalysts calcined at different temperature
图 4 不同焙烧温度复合催化剂的H2-TPR谱图
Figure 4 H2-TPR profiles of the composite catalysts calcined at different temperature
图 5 不同焙烧温度复合催化剂循环吸附性能
Figure 5 CO2 cyclic sorption performance of the composite catalysts calcined at different temperature
图 6 复合催化剂cat-700首次CO2吸附强化CH4/H2O重整反应性能
Figure 6 Catalytic performance of cat-700 for the CO2 sorption enhanced methane steam reforming in the first cycle
图 7 复合催化剂cat-700的10次CO2吸附强化CH4/H2O重整反应的H2和CO2浓度
Figure 7 H2 and CO2 concentration variation during 10 runs of the CO2 sorption enhanced steam methane reforming over the composite catalyst cat-700
表 1 不同焙烧温度复合催化剂的金属分散度与颗粒粒径
Table 1 Metal dispersion and particle size of the composite catalysts calcined at different temperature
Sample Metal surface area A/(m2·g-1) a Metal dispersion/%a CaO particle size d/nmb Ni particle size d/nmb Cat-700 11.95 1.79 36.89 19.51 Cat-750 9.72 1.46 38.03 24.42 Cat-800 7.13 1.07 40.12 28.81 Cat-850 5.92 0.98 39.49 33.73 a: calculated from H2-chemisorption; b: calculated from XRD results 
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表 2 不同焙烧温度复合催化剂的比表面积和孔结构
Table 2 BET specific surface area and pore structure of the composite catalysts calcined at different temperature
Sample BET specific surface area A/(m2·g-1) Total pore volume v/(cm3·g-1) Pore radius d/nm Cat-700 21.42 0.099 35.81 Cat-750 14.57 0.054 33.62 Cat-800 12.92 0.048 31.59 Cat-850 12.30 0.043 30.42
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