铜基载氧体的焦炉煤气化学链燃烧特性  

Combustion characteristics of coke oven gas chemical looping ofcopper-based oxygen carrier

作　　者：范心瑜 卢春强 左慧琮 李志强[1,2] 江磊[1,2] 李孔斋 FAN Xinyu;LU Chunqiang;ZUO Huicong;LI Zhiqiang;JIANG Lei;LI Kongzhai(Faculty of Metallurgical and Energy Engineering,Kunming University of Science and Technology,Kunming 650093,China;Engineering Research Center of Metallurgical Energy Conservation and Emission Reduction,Ministry of Education,Kunming 650093,China)

机构地区：[1]昆明理工大学冶金与能源工程学院,云南昆明650093 [2]冶金节能减排教育部工程研究中心,云南昆明650093

出　　处：《洁净煤技术》2024年第2期244-256,共13页Clean Coal Technology

基　　金：国家自然科学基金资助项目(52174279);昆明理工大学分析测试基金资助项目(2022M20212202022)。

摘　　要：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、H_(2)、CH_(4)、CO_(2)),化学链燃烧是一种可实现COG高效转化与高纯CO_(2)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Ce_(0.67)Zr_(0.33)O_(2)固溶体组成。由于Zr^(4+)进入CeO_(2)晶格中,在617 cm^(-1)处出现明显的氧空位Raman特征峰。H_(2)-TPR、CO-TPR、CH_(4)-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CO_(2)捕集率为34%,添加10%Ce_(0.67)Zr_(0.33)O_(2)后CO_(2)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Ce_(0.67)Zr_(0.33)O_(2)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 as CO,H_(2),CH_(4),and CO_(2).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 a solid solution of CuO and Ce_(0.67)Zr_(0.33)O_(2).Due to the incorporation of Zr 4+ions into the CeO_(2) lattice,a distinct oxygen vacancy Raman characteristic peak appears at 617 cm-1.H_(2)-TPR,CO-TPR,CH_(4)-TPR,and COG-TPR results suggest that the addition of Ce-Zr-O solid solution enhances the low-temperature oxygen release capacity of copper species.Under conditions of 800℃,the CO_(2) capture rate of the CuO sample is 34%,which increases to 100%with the addition of 10% Ce_(0.67)Zr_(0.33)O_(2).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 remain largely unchanges.This indicates that the interaction between CuO and Ce_(0.67)Zr_(0.33)O_(2) enhances the oxygen release capacity and cycling stability of copper species.This research contributes to expanding the utilization pathways of COG.

关 键 词：焦炉煤气 化学链燃烧 循环反应性能 CO_(2)捕集 

分 类 号：TQ519[化学工程]