焦炉煤气(COG)是炼焦过程产生的主要副产品,含有复杂的气体成分(CO、H2、CH4、CO2),化学链燃烧是一种可实现COG高效转化与高纯CO2捕集的技术。通过溶胶凝胶法制备了一系列x%CuO/Ce-Zr-O(x=30、50、70、90)载氧体用于COG化学链燃烧反应特性研究。XRD表明,x%CuO/Ce-Zr-O载氧体物相由CuO和Ce0.67Zr0.33O2固溶体组成。由于Zr4+进入CeO2晶格中,在617cm-1处出现明显的氧空位Raman特征峰。H2-TPR、CO-TPR、CH4-TPR和COG-TPR结果表明加入Ce-Zr-O固溶体促使铜物种低温释氧能力增强。800℃下,CuO样品CO2捕集率为34%,添加10%Ce0.67Zr0.33O2后CO2捕集率增至100%。经50次氧化还原循环后,CuO样品性能大幅降低,而90CuO/Ce-Zr-O样品的反应性能和物相结构未发生明显变化,表明CuO和Ce0.67Zr0.33O2之间的相互作用增强了铜物种的释氧能力和循环稳定性。此研究有助于拓宽COG利用途径。

Coke oven gas (COG) is a major byproduct generated during the coking process, containing complex gas components such asCO, H2, CH4, and CO2. Chemical looping combustion is a technology that efficiently converts COG and captures high-purity carbon dioxide. A series of x% CuO/ Ce-Zr-O (x= 30, 50, 70, 90) oxygen carriers were prepared using the sol-gel method for the study of chemical looping combustion characteristics of COG. XRD analysis indicates that the phases of x% CuO/ Ce-Zr-O oxygen carriers consist of asolid solution of CuO and Ce0.67Zr0.33O2. Due to the incorporation of Zr4+ ions into the CeO2 lattice, a distinct oxygen vacancy Raman characteristic peak appears at 617 cm-1. H2-TPR, CO-TPR, CH4-TPR, and COG-TPR results suggest that the addition of Ce-Zr-O solidsolution enhances the low-temperature oxygen release capacity of copper species. Under conditions of 800 ℃ , the CO2 capture rate of theCuO sample is 34%, which increases to 100% with the addition of 10% Ce0.67Zr0.33O2. After 50 cycles of oxidation-reduction, the performance of the CuO sample significantly deteriorates, while the reactivity and phase structure of the 90CuO/ Ce-Zr-O sample remainlargely unchanges. This indicates that the interaction between CuO and Ce0.67Zr0.33O2 enhances the oxygen release capacity and cycling stability of copper species. This research contributes to expanding the utilization pathways of COG.

0 引言

1 试验

   1.1 载氧体制备

   1.2 载氧体物理化学表征

   1.3 微观形貌分析

   1.4 程序升温还原

   1.5 载氧体恒温反应活性评价

2 结果与讨论

   2.1 载氧体物理化学表征

   2.2 程序升温还原

   2.3 载氧体恒温反应活性评价

   2.4 微观形貌分析

   2.5 载氧体循环前后的物性结构变化

3 结论