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    镍基双功能材料CO2捕集与原位甲烷化研究进展

    Research Progress on Integrated CO2 Capture and Methanation Using Nickel-Based Dual-Function Materials

    • 摘要: 集成CO2捕集与甲烷化(ICCM)技术可为我国实现“双碳”目标提供重要的技术支撑,是前沿研究的热点。该技术将CO2捕集与催化转化过程耦合,在单一反应器中实现CO2的捕集并原位转化为高附加值甲烷,具有能耗低、流程短、效率高等显著优势。系统综述了镍基双功能材料(DFMs)在ICCM技术中的研究进展,重点围绕材料设计、性能优化及实际应用挑战展开深入分析。系统阐述了不同类型吸附剂(包括钙基、镁基和碱金属基等)的设计策略与性能特征,总结了助剂掺杂(如Ru、Zr和Ce等)、操作条件(反应温度与压力、H2浓度、空度和杂质组分)优化等对提升CO2捕集与甲烷化效率的作用;深入探讨了O2、H2O、NOx、SO2等真实烟气组分对ICCM反应的影响及失活机制。最后,对该领域研究方向进行了展望,未来应致力于高效DFMs的设计、真实气氛下失效机制的深入解析及多污染物协同控制等关键科学和工程问题的研究,以推动ICCM技术从实验室向规模化应用发展。

       

      Abstract: Integrated carbon dioxide (CO2) capture and methanation (ICCM) is a crucial technology for achieving carbon neutrality, as it converts waste CO2 into synthetic natural gas through the utilization of dual-functional materials (DFMs). This review systematically synthesizes recent progress in nickel-based DFMs, aiming to clarify the relationships among material design, reaction mechanisms in complex flue gas environments, and engineering challenges associated with process scale-up. The discussion covers various synthesis strategies for adsorbents, including calcium-, magnesium-, and alkali metal-based systems. It critically examines the roles of promoters as well as the influence of reactor configuration and operational parameters. Emphasis is placed on multi-scale structural effects, ranging from macroscopic bed configurations to nanoscale interfacial engineering. Furthermore, deactivation mechanisms caused by realistic flue gas components such as O2, H2O, NOx, and SO2 are thoroughly summarized. In terms of material optimization, while CaO-based DFMs exhibit exceptional theoretical capacities, their real-world applications are frequently hindered by sintering and thermodynamic limitations. Strategies such as the incorporation of inert supports (e.g., γ-Al2O3), the use of layered double hydroxide (LDH) precursors, and alkali-metal doping have proven effective in enhancing component dispersion and cyclic stability. Similarly, MgO-based materials, which often suffer from surface passivation, show significantly improved CO2 uptake kinetics through the addition of alkali nitrate molten salts. Moreover, the review highlights the important roles played by transition-metal promoters (such as Ru, Zr, Ce) in facilitating low-temperature reduction, refining Ni crystallite size, and generating oxygen vacancies (Ovs) or frustrated Lewis pairs (FLPs) that enhance surface activation. A critical analysis reveals that the proximity between adsorption and catalytic sites is paramount in determining overall reaction efficiency. Constructing nanoscale interfaces with buffer layers (e.g., CeO2, AlOx) or employing core-shell structures can proficiently balance mass-transfer efficiency with active site accessibility. Regarding the influence of impurities, the presence of O2 leads to temporary Ni oxidation, which can assist in coke removal; however, H2O and NOx impede the process through competitive adsorption. Notably, SO2 acts as a significant poison, forming stable sulfates that occupy basic sites and kinetically inhibit the decomposition of critical formate (HCOO*) intermediates, thus blocking hydrogenation pathways. This review also concludes that the successful industrial implementation of ICCM technology requires a shift in emphasis from laboratory-scale material screening toward integrated engineering-system design. Future research should focus on: (1) the development of highly active, stable, and anti-toxic DFMs; (2) the elucidation of deactivation mechanisms in complex atmospheres using in situ characterization techniques; (3) the design of synergistic multi-pollutant control strategies, such as integrated CO2/SO2 and CO2/NOx treatment systems; and (4) the engineering of specialized reactors capable of handling the rapid thermal cycling and strongly exothermic nature of the ICCM process.

       

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