Influence of preparation method on the structure of NiCo/MgO catalyst and its performance in the reforming of CH4 with CO2
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摘要: 为进一步提高镍基催化剂的抗积炭能力，增强其甲烷二氧化碳重整反应性能，采用沉积沉淀法（DP）、共沉淀法（CP）和共浸渍法（CI）制备了NiCo/MgO催化剂。结合现代仪器分析表征技术，研究了制备方法对NiCo/MgO催化剂结构和抗积炭能力的影响。结果表明，与共沉淀法相比，沉积沉淀法制备过程为Ni2+和Co2+的完全水解沉淀提供了碱性环境，粒子的成核和生长速率相对较快，不存局部过饱和现象，所制备的催化剂具有良好的还原性、较小的颗粒粒径（9.7 nm）、良好的Ni/Co分散度（10.4%）和大的比表面积（68.1 m2/g），从而具有优良的抗积炭性能。对于甲烷二氧化碳重整，DP催化剂上CH4和CO2转化率保持在88%和92%，与800℃下的热力学平衡转化率相近；同时，H2收率比CP和CI催化剂分别高约10%和43%，CO收率比CP和CI催化剂分别高约13%和42%，且稳定性更好。Abstract: To enhance the performance of nickel-based catalysts in the reforming of CH4 with CO2 and alleviate the coke deposition, a series of NiCo/MgO catalysts were prepared by different methods, viz., deposition-precipitation (DP), co-precipitation method (CP) and co-impregnation (CI); the influence of preparation method on the structure and performance of NiCo/MgO catalyst was then investigated. The results show that during the deposition-precipitation process, CO(NH2)2 as the precipitant could created an alkaline atmosphere for the complete hydrolysis of Ni2+ and Co2+ ions, leading to a relatively fast nucleation and growth of active species; however, oversaturation may occur during the co-precipitation process with NaOH and Na2CO3 as the precipitants. In comparison with the catalysts prepared by CP and CI, the NiCo/MgO-DP catalyst is provided with superior reduction capacity, smaller particle size (9.7 nm), higher Ni/Co dispersion (10.4%) and larger specific surface area (68.1 m2/g) and then exhibits better resistance to coke deposition. Over the DP catalyst, the conversions of CH4 and CO2 at 800 ℃ reach 88% and 92%, respectively, much higher than those over the CP and CI catalysts; moreover, the DP catalyst also gives much higher yield of H2 and CO as well as better stability for methane reforming with CO2.
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Key words:
- methane reforming with CO2 /
- preparation method /
- Ni /
- Co /
- MgO /
- deposition-precipitation /
- co-precipitation method /
- co-impregnation
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图 2 还原后催化剂的XRD谱图
Figure 2 XRD patterns of the reduced NiCo/MgO catalysts synthesized by different methods
a: deposition-precipitation method; b: co-precipitation method; c: co-impregnation method
图 3 不同制备方法催化剂的H2-TPR谱图
Figure 3 H2-TPR profiles of the NiCo/MgO catalysts synthesized by different methods
a: deposition-precipitation method; b: co-precipitation method; c: co-impregnation method
图 4 不同方法制备催化剂CH4-CO2重整CH4转化率和H2收率
Figure 4 CH4 conversion and H2 yield versus time on stream for CH4-CO2 reaction at 800 ℃ over the NiCo/MgO catalysts synthesized by different methods
a: deposition-precipitation method; b: co-precipitation method; c: co-impregnation method
图 5 不同方法制备催化剂CH4-CO2重整CO2转化率和CO收率
Figure 5 CO2 conversion and CO yield versus time on stream for CH4-CO2 reaction at 800 ℃ over the NiCo/MgO catalysts synthesized by different methods
a: deposition-precipitation method; b: co-precipitation method; c: co-impregnation method
图 6 反应后不同制备方法催化剂的TGA曲线
Figure 6 TGA curves of the spent NiCo/MgO catalysts synthesized by different methods
a: deposition-precipitation method; b: co-precipitation method; c: co-impregnation method
表 1 不同制备方法NiCo/MgO催化剂的元素组成
Table 1 Element composition of the NiCo/MgO catalysts synthesized by different methods
表 2 不同制备方法催化剂金属分散度与颗粒粒径
Table 2 Metal dispersion and particle size of the NiCo/MgO catalysts synthesized by different methods
表 3 不同制备方法催化剂的比表面积和孔结构
Table 3 BET specific surface area and pore structure of the NiCo/MgO catalysts synthesized by different methods
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