CeO<sub>2</sub>掺杂对CaO基吸收剂CO<sub>2</sub>捕获性能的影响

杨彬; 余钟亮; 李春玉; 周兴; 郭帅; 李光; 赵建涛; 房倚天

CeO₂掺杂对CaO基吸收剂CO₂捕获性能的影响

杨彬^{1, 2},
余钟亮^1, ,,
李春玉¹,
周兴^{1, 2},
郭帅^{1, 2},
李光^{1, 2},
赵建涛^1, ,,
房倚天¹

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049

基金项目:

国家重点研发计划 2018YFB0605401-03

详细信息

中图分类号: X701
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- 文章访问数: 106
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- 被引次数: 0
出版历程
- 收稿日期: 2018-12-21
- 修回日期: 2019-01-22
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-03-10

Influence of cerium doping on CO₂ capture of CaO-based sorbents

YANG Bin^{1, 2},
YU Zhong-liang^{1
, ,},
LI Chun-yu¹,
ZHOU Xing^{1, 2},
GUO Shuai^{1, 2},
LI Guang^{1, 2},
ZHAO Jian-tao^{1
, ,},
FANG Yi-tian¹

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds:

The project was supported by the National Key Research and Development Program of China 2018YFB0605401-03

More Information

Corresponding author: YU Zhong-liang, E-mail: yuzl@sxicc.ac.cn; ZHAO Jian-tao, Tel/Fax: 0351-2021137, E-mail: zhaojt@sxicc.ac.cn

摘要

摘要: 以P123作为软模板剂，通过均相沉淀法制备了CeO₂掺杂的CaO基吸收剂，研究了CeO₂掺杂对CO₂捕获的影响。结果表明，CeO₂掺杂可促进表面氧物种的生成，从而促进CaO与CO₂的碳酸化反应。CaO-CeO₂的相互作用一方面促进了从Ca到表面氧物种的电子转移；另一方面，由于部分Ca离子对晶格中Ce离子的取代，晶格的电中性被打破，有利于CeO₂中晶格氧的逸出，以及氧空位和O^2-的生成。本实验制备的纯CaO吸收剂的碳酸化反应活化能为28.1 kJ/mol，而掺杂CeO₂后活化能显著降低，且当Ce/Ca（物质的量比）为0.25时达到最低值10.2 kJ/mol。另外，CeO₂的掺杂有利于CaO的分散，进而减缓CaO烧结。CeO₂掺杂的吸收剂在碳酸化/煅烧循环中表现出良好的CO₂捕获性能和循环稳定性。
- CaO基吸收剂 /
- CO₂捕获 /
- CeO₂掺杂 /
- 碳酸化
Abstract: The CeO₂-doped CaO-based sorbent was prepared by the homogeneous precipitation method using P123 as the soft template. The influence of CeO₂ doping on the capture of CO₂ was investigated. The CeO₂ doping can promote the formation of surface oxygen species, and facilitate the carbonation reaction. The interactions in CaO-CeO₂ lead to the electrons transfer from Ca to surface oxygen species. Moreover, when Ce ions are substituted by Ca ions, the charge neutrality is destroyed in the CeO₂ crystal, which promotes the formation of oxygen vacancies and O^2-. E_a is tested to be 28.1 kJ/mol for the carbonation reaction of pure CaO sorbent, while E_a decreases to the minimal value of 10.2 kJ/mol when adding CeO₂ to CaO sorbent with a Ce/Ca molar ratio of 0.25. Also, the doping of CeO₂ is beneficial to the high dispersion of CaO and prevention of CaO sintering. The Ce-doped sorbents exhibit a superior capture capacity and cyclic stability in carbonation/calcination cycles.
- CaO-based sorbent /
- CO₂ capture /
- CeO₂-doped /
- carbonation

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图 1 CaO-CeO₂吸收剂的碳酸化转化率

Figure 1 Carbonation conversion of CaO-CeO₂ sorbents

a: Ce/Ca_0; b: Ce/Ca_1; c: Ce/Ca_0.5; d: Ce/Ca_0.25

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图 2 CaO-CeO₂吸收剂的CO₂吸收量

Figure 2 CO₂ uptake of CaO-CeO₂ sorbents

a: Ce/Ca_1; b: Ce/Ca_0.5; c: Ce/Ca_0.25; d: Ce/Ca_0

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图 3 CaO-CeO₂吸收剂的XRD谱图

Figure 3 XRD patterns of CaO-CeO₂ sorbents

a: Ce/Ca_0; b: Ce/Ca_0.25; c: Ce/Ca_0.5; d: Ce/Ca_1

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图 4 CaO-CeO₂吸收剂的N₂吸附-脱附和孔径分布

Figure 4 N₂ adsorption/desorption isotherms (a) and pore size distributions of CaO-CeO₂ sorbents (b)

a: Ce/Ca_0; b: Ce/Ca_0.25; c: Ce/Ca_0.5; d: Ce/Ca_1

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图 5 CaO-CeO₂吸收剂的拉曼光谱谱图

Figure 5 Raman spectra of CaO-CeO₂ sorbents

a: Ce/Ca_0; b: Ce/Ca_0.25; c: Ce/Ca_0.5; d: Ce/Ca_1

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图 6 CaO-CeO₂吸收剂的O 1s和Ca 2p的XPS谱图

Figure 6 XPS spectra of O 1s and Ca 2p of CaO-CeO₂ sorbents

a: Ce/Ca_0; b: Ce/Ca_0.25; c: Ce/Ca_0.5; d: Ce/Ca_1

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图 7 Ce/Ca_0.25吸收剂的EDS谱图

Figure 7 EDS of Ce/Ca_0.25 sorbents

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图 8 (a) F(x)-t曲线和(b)Arrhenius曲线

Figure 8 (a) F(x) vs t and (b) Arrhenius plots

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图 9 活化能随CeO₂/CaO物质的量比的变化

Figure 9 Variation of activation energy with Ce/Ca molar ratios

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