Research on doping modification and morphology control of calcium-based CO2 sorbents

doi:10.16085/j.issn.1000-6613.2018-1340

Abstract

Abstract:

Carbon capture/storage (CCS) is of great significance to solve the problems of greenhouse effect, climate warming, environmental pollution and energy crisis. More attention has been paid on Ca-based sorbents because their high adsorption capacity and lower cost. The characteristics and adsorption mechanism of calcium-based CO₂ sorbents are introduced. This paper focuses on two modification methods of calcium-based sorbents, including incorporation of refractory metals into CaO and morphology modification, which are effective to improve the stability. Single and co-doping by metal oxides with high Tamman temperatures or more oxygen vacancies, such as Zr, Ce, Mn, Mg, Al, are introduced. The influence of synthetic methods, conditions of adsorption-desorption, content of inert material, and the precursor on the performance of calcium-based sorbents is discussed. The hollow and solid spherical particles of calcium-based sorbents prepared by polystyrene beads, carbon aerogels, and carbon sphere, have favorable adsorption capacity and stability. However, there is still a long way to go for realizing the industrial application. It is urgent to explore the relationship between the structure and the performance, so as to provide the theoretical guidance.

Key words: CO₂ adsorption, calcium-based sorbent, modification, doping, morphology

摘要：

有效捕集CO₂对于缓解亟待解决的温室效应、气候变暖、环境污染和能源危机问题具有重大意义。钙基吸附材料因为CO₂吸附容量高及成本低廉而受到了广泛关注。本文介绍了钙基吸附剂的CO₂吸附机理，着重阐述了显著提高吸附性能的两种改性方法，包括惰性掺杂和形貌调控。归纳了利用Zr、Ce、Mn、Mg、Al等塔曼温度较高或富含氧空穴的金属氧化物对氧化钙进行单掺杂和复合掺杂改性，针对合成方法、吸脱附条件、惰性组分掺杂量、钙基前体等不同参数对掺杂改性钙基CO₂吸附剂性能的影响进行总结。同时指出，采用聚苯乙烯小球、碳凝胶、碳球、表面活性剂等制备得到的中空结构球形钙基吸附剂或实心结构球形钙基吸附剂，具有良好的CO₂吸附容量和吸附稳定性。提出两种改性方法距离工业化应用还有较大的差距，亟需深入探讨吸附剂的结构与性能之间的关系，从而为吸附剂的设计提供理论指导。

关键词: CO₂吸附, 钙基吸附剂, 改性, 掺杂, 形貌

CLC Number:

TQ028

Hongxia GUO, Yan NAN, Xiaochen KOU, Shengping WANG, Yujun ZHAO, Xinbin MA. Research on doping modification and morphology control of calcium-based CO₂ sorbents[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 457-466.

郭红霞, 南雁, 寇晓晨, 王胜平, 赵玉军, 马新宾. 钙基CO₂吸附剂的惰性掺杂和形貌调控研究进展[J]. 化工进展, 2019, 38(01): 457-466.

Figures/Tables 1

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掺杂量 Ca/Zr（摩尔比）	制备方法	吸脱附温度/℃	循环次数	反应器	吸附容量/g·g^-1	参考文献
10/3	火焰喷雾法	700/700	100	TGA	64%（X _CaO）	[6]
10/5	火焰喷雾法	700/700	1200	TGA	60%（X _CaO）	[7]
10/1	湿混合	650/930	25	IGA	0.30	[8]
30/1	湿化学法	650/800	30	TGA	0.37	[9]
13.2/1	溶胶-凝胶法	650/900	30	TGA	0.45	[10]
95/5	溶胶-凝胶法	800/800	90	TGA	0.34	[11]
8.5/1	高温固相法	650/700	20	TGA	0.48	[12]
3.3/1	表面活性剂模板/超声法	600/750	15	TGA	0.15	[13]
10/5	溶胶-凝胶法	700/700	1200	TGA	0.30	[14]

掺杂量 Ca/Zr（摩尔比）	制备方法	吸脱附温度/℃	循环次数	反应器	吸附容量/g·g^-1	参考文献
10/3	火焰喷雾法	700/700	100	TGA	64%（X _CaO）	[6]
10/5	火焰喷雾法	700/700	1200	TGA	60%（X _CaO）	[7]
10/1	湿混合	650/930	25	IGA	0.30	[8]
30/1	湿化学法	650/800	30	TGA	0.37	[9]
13.2/1	溶胶-凝胶法	650/900	30	TGA	0.45	[10]
95/5	溶胶-凝胶法	800/800	90	TGA	0.34	[11]
8.5/1	高温固相法	650/700	20	TGA	0.48	[12]
3.3/1	表面活性剂模板/超声法	600/750	15	TGA	0.15	[13]
10/5	溶胶-凝胶法	700/700	1200	TGA	0.30	[14]

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Research on doping modification and morphology control of calcium-based CO₂ sorbents

钙基CO₂吸附剂的惰性掺杂和形貌调控研究进展

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