Study of CeO2/LaFeO3 in chemical looping reforming of methane for syngas production
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摘要: 甲烷化学链重整是一种利用载氧体（金属氧化物）的部分氧化能力以实现甲烷重整制取合成气的工艺，同时氧化过程中利用水蒸气氧化，还原态的载氧体在恢复晶格氧的同时分解水蒸气制氢。利用溶胶-凝胶法制备载氧体CeO2/LaFeO3，通过X射线粉末衍射和程序升温还原等材料表征方法分析该载氧体的结构特点以及供氧能力，借助于固定床反应实验探讨了组分比例、反应温度对该载氧体反应性能的影响。实验结果表明，CeO2的含量对该载氧体的供氧能力有着显著影响，合适的反应温度不仅有利于甲烷活化，而且能够促进载氧体中晶格氧的迁移，从而提高载氧体的选择性。当CeO2的添加量为10%，反应温度为850 ℃时，该载氧体的反应性能最优，甲烷转化率可以达到94%，H2选择性和CO选择性分别可以达到90%、83%。在连续的氧化-还原循环中保持稳定的反应性能和结构。Abstract: Chemical looping methane reforming is a potential route to co-produce syngas and hydrogen by using the oxygen carrier (metal oxide). The oxygen carrier CeO2/LaFeO3 was prepared by sol-gel method, and the structure and oxygen supply capacity of the oxygen carrier were analyzed by X-ray powder diffraction and hydrogen temperature programmed reduction. The influence of CeO2 ratio and reaction temperature on the performance of the oxygen carrier were discussed through fixed bed reaction tests. The content of CeO2 had a significant effect on the oxygen supply capacity of the oxygen carrier. Increasing reaction temperature not only was conducive to methane activation, but also enhanced lattice oxygen migration in the oxygen carrier. A suitable reaction temperature could match methane activation with lattice oxygen migration, thereby improving the selectivity of the oxygen carrier. Experimental results showed that performance of the oxygen carrier was in the optimal when CeO2 content was 10% and reaction temperature was 850 ºC. CH4 conversion rate could reach 94%, H2 selectivity and CO selectivity could reach 90% and 83%, respectively. The oxygen carrier 10%CeO2/LaFeO3 could maintain stable reaction performance and structure in the redox cycles.
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Key words:
- methane /
- chemical looping reforming /
- syngas /
- oxygen carrier /
- selectivity
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图 3 载氧体的XRD、H2-TPR表征
Figure 3 XRD, H2-TPR results of characterization of oxygen carriers
图 4 CeO2含量对载氧体反应性能的影响
Figure 4 Influence of CeO2 content on the performance of oxygen carriers
图 5 反应温度对10CLFO的反应性能的影响
Figure 5 Influence of reaction temperature on the performance of 10CLFO
图 8 固定床循环反应性能
Figure 8 Results of fixed bed redox cycles
(a): Methane reforming reaction products distribution; (b): Performance evaluation of methane reforming reaction; (c): Steam oxidation product distribution; (d): XRD of 10CLFO after reaction
表 1 氧物种相对含量
Table 1 Contents of different oxygen species
Sample OI/% OII/% OIII/% OLat /Oads 10CLFO 49.05 46.55 4.40 0.96 10CLFO-750 50.44 44.7 4.86 1.02 10CLFO-850 16.65 70.13 13.22 0.20 10CLFO-900 13.79 74.02 12.19 0.16 
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