Fe x Co y Ca3Al双功能材料用于CO2捕集-转化一体化制合成气

doi:10.16085/j.issn.1000-6613.2024-1845

摘要/Abstract

摘要：

二氧化碳（CO₂）的大量排放是导致全球变暖的主要原因之一，其中CO₂捕集、利用与封存（CO₂ capture, utilization and storage，CCUS）技术是减少碳排放的关键手段，然而传统CCUS技术中捕集成本较高，限制了CCUS技术的推广应用。本文采用CO₂捕集-转化一体化（integrated carbon capture and conversion，ICCC）技术方案，通过将碳捕集过程与碳转化过程相耦合，避免CO₂捕集材料再生所需的大量能耗，从而降低CCUS捕集过程成本。实验以Fe、Co基非贵金属作为催化组分，Ca为吸附组分，采用并流共沉淀的方法制备了Fe _x Co _y Ca₃Al系列双功能材料，应用于ICCC制备合成气过程，探究了Fe/Co对双功能材料性能的影响，通过透射电子显微镜、X射线光电子能谱、H₂-程序升温还原、CO₂-程序升温脱附等对双功能材料进行表征，相关结果表明双功能材料Fe、Co、Ca、Al等元素分布均匀，未出现团聚现象，Fe-Co元素之间存在相互作用，提升了双功能材料的一体化性能。在优化条件下，Fe_0.5Co_0.5Ca₃Al材料CO₂捕集容量为11.05mmol/g，CO产率达到11.94mmol/(g∙h)。

关键词: CO₂捕集-转化一体化, 逆水煤气变换, 合成气, 双功能材料, 温室气体, 催化剂

Abstract:

The massive emission of CO₂ is one of the primary reasons behind global warming. CO₂ capture, utilization and storage (CCUS) technology stands as a pivotal means to reduce CO₂ emissions. However, the high capture costs in CCUS technology limit its widespread application. This study employed an Integrated Carbon Capture and Conversion (ICCC) technology, which coupled the capture process with the conversion process, thereby avoiding the substantial energy consumption required for the regeneration of CO₂ capture materials and reducing the cost of the CCUS capture process. The experiment utilized non-precious metals based on Fe and Co as catalytic components and Ca as the adsorption component. A series of Fe _x Co _y Ca₃Al dual-functional materials were prepared using a co-current co-precipitation method for application in the ICCC process for syngas production. The influence of the Fe/Co ratio on the performance of the dual-functional materials was investigated. The dual-functional materials were characterized using techniques such as TEM, XPS, H₂-TPR and CO₂-TPD. The relevant results indicated that the elements Fe, Co, Ca and Al in the dual-functional materials were uniformly distributed without aggregation. There was an interaction between Fe and Co elements, enhancing the integrated performance of the dual-functional materials. Under optimized conditions, the Fe_0.5Co_0.5Ca₃Al material exhibited a CO₂ capture capacity of 11.05mmol/g and a CO yield of 11.94mmol/(g∙h).

Key words: integrated carbon capture and conversion, reverse water gas shift reaction, synthesis gas, dual-function materials, greenhouse gas, catalyst

中图分类号:

X701

汪柯, 胡登, 王星博, 孙楠楠, 魏伟. Fe _x Co _y Ca₃Al双功能材料用于CO₂捕集-转化一体化制合成气[J]. 化工进展, 2025, 44(5): 2888-2897.

WANG Ke, HU Deng, WANG Xingbo, SUN Nannan, WEI Wei. Using Fe _x Co _y Ca₃Al dual-functional material on integrated CO₂ capture and conversion to syngas[J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2888-2897.

图/表 14

图1 Fe x Co y Ca3Al系列双功能材料的XRD谱图

图2 Fe0.5Co0.5Ca3Al双功能材料的TEM图

图3 Fe x Co y Ca3Al系列双功能材料

表1 Fe x Co y Ca3Al系列双功能材料的比表面积、孔容和孔径

双功能材料	比表面积 /m²·g^-1	孔容 /cm³·g^-1	平均孔径 /nm
Co₁Ca₃Al	6.0	0.024	2.58
Fe_0.25Co_0.75Ca₃Al	6.0	0.023	2.32
Fe_0.5Co_0.5Ca₃Al	4.7	0.021	3.16
Fe_0.75Co_0.25Ca₃Al	3.5	0.007	2.32
Fe₁Ca₃Al	6.6	0.018	3.90

表2 Fe x Co y Ca3Al催化剂的元素质量分数

双功能材料	元素质量分数/%
双功能材料	Ca	Fe	Co
Co₁Ca₃Al	53.57	0.01	14.66
Fe_0.25Co_0.75Ca₃Al	58.24	2.93	7.96
Fe_0.5Co_0.5Ca₃Al	57.76	6.51	6.29
Fe_0.75Co_0.25Ca₃Al	58.24	9.51	3.18
Fe₁Ca₃Al	56.26	14.73	0.02

图4 Fe x Co y Ca3Al的XPS谱图

图5 双功能材料的H2-TPR谱图

图6 双功能材料的CO2-TPD谱图

图7 Fe x Co y Ca3Al系列双功能材料的TG曲线

表3 Fe x Co y Ca3Al系列双功能材料的CO2捕集性能表

双功能材料	吸附总量/mmol∙g^-1
Co₁Ca₃Al	10.27
Fe_0.25Co_0.75Ca₃Al	10.91
Fe_0.5Co_0.5Ca₃Al	11.42
Fe_0.75Co_0.25Ca₃Al	10.81
Fe₁Ca₃Al	9.33

图8 Fe x Co y Ca3Al系列双功能材料ICCC制备合成气过程气体MS信号变换趋势

图9 Fe x Co y Ca3Al系列双功能材料一体化性能图

图10 Fe0.5Co0.5Ca3Al材料的循环稳定性测试气体MS信号变化趋势

图11 Fe0.5Co0.5Ca3Al材料的循环稳定性能

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Fe _x Co _y Ca₃Al双功能材料用于CO₂捕集-转化一体化制合成气

Using Fe _x Co _y Ca₃Al dual-functional material on integrated CO₂ capture and conversion to syngas

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