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    高温钙基固体吸附CO2捕集技术研究进展

    Research progress in high−temperature calcium-based sorbents for CO2 capture

    • 摘要: 在全球气候变化和“双碳”目标的推动下,碳捕集、利用与封存(CCUS)技术成为工业领域实现温室气体减排的关键。高温钙基固体吸附CO2捕集技术因成本低、吸附容量高而备受关注,然而CaO吸附剂在循环过程中易烧结、磨损,致使性能衰减,限制了其规模化应用。综述了近年来CaO吸附剂的改性方法、规模化制备工艺、反应器设计以及钙循环中试装置的研究进展。在改性方法上,有机酸、碱金属盐、生物质衍生材料、金属氧化物及固体废弃物等均可用于改性CaO吸附剂,例如,丙酸改性的石灰石在100次循环后CO2捕集能力为未处理样品的4倍。吸附剂颗粒制备技术包括挤压法、滚圆法、挤压–滚圆法、浇铸法、核壳法等,不同方法制备的颗粒在机械强度、CO2捕集能力等方面各有差异。例如,挤压−滚圆法结合喷雾干燥技术制备的吸附剂微球,25次循环后CO2吸附量较高且抗磨损能力强,旋转3000次后的失重率低于0.8%。在反应器方面,流化床反应器应用最为广泛,但存在颗粒磨损的问题;移动床反应器可缩小反应器尺寸,但存在阻力的问题。另外,多个国家和地区的中试装置验证了钙循环CO2捕集技术的可行性,如德国斯图加特的200 kWh平台、西班牙La Pereda的1.7 MWh平台等,可实现约90%的CO2捕集效率。最后,指出未来需突破低成本规模化制备工艺,解决现有成型技术原材料成本高、成品率低等问题;优化反应器传热传质性能;推进构建余热梯级利用的能量集成系统,降低捕集能耗,从而推动CaO吸附剂CO2捕集技术从工程验证迈向工业化应用的关键跨越。

       

      Abstract: Driven by global climate change and the “carbon peaking and carbon neutrality” goals, carbon capture, utilization, and storage (CCUS) technology has become pivotal for achieving greenhouse gas emissions reduction in industrial sectors. High-temperature calcium-based solid adsorption CO2 capture technology has garnered significant attention due to its low cost and high adsorption capacity. However, CaO sorbents are prone to sintering and abrasion during cyclic operations, leading to performance degradation and hindering their large-scale deployment. The modification methods, large-scale preparation processes, reactor design, and pilot-scale calcium looping systems of CaO adsorbent in recent years are reviewed. Regarding modification strategies, organic acids, alkali metal salts, biomass-derived materials, metal oxides, and solid waste residues have all been employed to enhance CaO performance. For instance, propionic acid-modified limestone demonstrates a CO2 capture capacity four times higher than untreated samples after 100 cycles. Particle preparation techniques for adsorbents include extrusion, spheronization, extrusion-spheronization, casting, and core-shell methods. These methods yield particles with varying mechanical strengths and CO2 capture efficiencies. The extrusion-spheronization combined with spray drying, for example, produces microspheres with high CO2 adsorption capacity (retaining efficiency after 25 cycles) and excellent abrasion resistance (weight loss <0.8% after 3 000 rotations). In reactor design, fluidized bed reactors are most widely used but suffer from particle attrition, while moving bed reactors reduce size but face pressure drop issues. Pilot-scale systems in multiple countries and regions have validated calcium looping technology, such as the 200 kWh platform in Stuttgart, Germany, and the 1.7 MWh facility in La Pereda, Spain, achieving around 90% CO2 capture efficiency. Future challenges include developing cost-effective large-scale production processes to address high raw material costs and low yields, optimizing reactor heat/mass transfer, and integrating waste heat cascade utilization systems to reduce energy consumption. Overcoming these hurdles will facilitate the transition of CaO-based CO2 capture from engineering demonstration to industrial application.

       

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