Preparation of porous calcium carbonate by salt template method and its CO2 adsorption characteristics

doi:10.11949/0438-1157.20250285

Abstract

Abstract:

CO₂ as one of the greenhouse gases has a significant impact on global climate change. It is crucial to develop efficient and economical CO₂ capture technologies. One potential approach is the adsorption of CO₂ using CaCO₃ due to its wide availability, low cost and the ability to optimize the adsorption properties by modulating the morphology and specific surface area. In this study, CaCO₃ materials were prepared using KCl, NaCl and LiCl as salt templates, and the CO₂ adsorption properties were systematically evaluated. The results showed that the specific surface area of CaCO₃-KCl was significantly higher than that of CaCO₃-NaCl and CaCO₃-LiCl, which were 72.6, 40.2 and 18.9 m²/g, respectively. The CaCO₃-KCl showed a porous nanosheet structure. The CO₂-TPD showed that the surface of CaCO₃-KCl possessed more adsorption sites. Importantly, the CO₂ adsorption amounts of CaCO₃-KCl, CaCO₃-NaCl and CaCO₃-LiCl were 0.39, 0.32 and 0.31 mmol/g, respectively. The CO₂ adsorption amount of CaCO₃-KCl only decreased by 7% in 10 breakthrough-cycling experiments and had a better separation effect on CO₂/N₂. The separation effect improved from 3.4 to 44.8. This study reveals the effects of salt templating agent on the morphology, specific surface area and CO₂ adsorption performance of CaCO₃, which provides an important reference for the design of efficient CO₂ adsorption materials.

Key words: salt templating agent, mechanical ball milling method, porous structure, CaCO₃, sorbents, carbon dioxide adsorption

摘要：

CO₂作为温室气体之一，对全球气候变化产生了显著影响。开发高效、经济的CO₂捕获技术至关重要。利用CaCO₃吸附CO₂是一种具有潜力的方法，其原料来源广泛、成本低廉且可通过调控形貌和比表面积优化吸附性能。本研究以KCl、NaCl和LiCl为盐模板制备了CaCO₃材料，并系统评估了其对CO₂的吸附性能。结果表明，CaCO₃-KCl的比表面积显著高于CaCO₃-NaCl和CaCO₃-LiCl，分别为72.6、40.2和18.9 m²/g。且CaCO₃-KCl呈现多孔纳米片结构。CO₂-TPD显示，CaCO₃-KCl表面具有较多的吸附位点。重要的是，CaCO₃-KCl、CaCO₃-NaCl和CaCO₃-LiCl的CO₂吸附量分别为0.39、0.32和0.31 mmol/g。CaCO₃-KCl在10次穿透循环实验中的CO₂吸附量仅降低了7%，并对CO₂/N₂有着较好的分离效果。本研究揭示了盐模板剂对CaCO₃形貌、比表面积及CO₂吸附性能的影响，为高效CO₂吸附材料的设计提供了重要参考。

关键词: 盐模板剂, 机械球磨法, 多孔结构, 碳酸钙, 吸附剂, 二氧化碳吸附

CLC Number:

TQ 132.3

Meiyu SHI, Bochen ZHAO, Yuan SHU, Qiang NIU, Pengfei ZHANG. Preparation of porous calcium carbonate by salt template method and its CO₂ adsorption characteristics[J]. CIESC Journal, 2025, 76(11): 6086-6099.

石美玉, 赵波琛, 束远, 牛强, 张鹏飞. 盐模板法制备多孔碳酸钙及其CO₂吸附特性研究[J]. 化工学报, 2025, 76(11): 6086-6099.

Figures/Tables 16

Fig.1 XRD spectra of intermediates from each step of synthesis of CaCO3

Fig.2 SEM images of samples at different stages

Fig.3 SEM images of porous CaCO3-XCl

Table 1 Specific surface area， pore volume and pore size of CaCO3-XCl

吸附剂	比表面积/ (m²/g)	孔容（BJH）/ (cm³/g)	孔径/nm
CaCO₃-KCl	72.6	0.25	14.04
CaCO₃-NaCl	40.2	0.19	18.50
CaCO₃-LiCl	13.7	0.06	26.87
CaCO₃-KCl（循环10次后）	55.2	0.23	13.04

Fig.4 N2 physical adsorption-desorption curves and BJH particle size distribution for CaCO3-XCl

Fig.5 TEM image of porous CaCO3 prepared using KCl as templating agent

Fig.6 Infrared spectrum of CaCO3-XCl

Fig.7 Raman spectra of CaCO3-XCl

Fig.8 Static CO2 adsorption properties of CaCO3 prepared with different template agents

Fig.9 Static CO2 adsorption performance and cyclic adsorption of CaCO3-XCl

Table 2 Comparison of cyclic stability of the adsorbents in this study with similar typical Ca-based adsorbents

吸附剂	吸附温度/℃	比表面积/(m²/g)	循环次数（吸附下降量）
CaCO₃-es^[37]	30	97.4	7次（6.0%）
ESCE-Ca9Y1^[38]	700	16.69	5次（30.3%）
CaCO₃-MgO^[39] AMS-MgCa5^[40]	280 340	230 177.2	10次（35.0%） 10次（28.8%）
CaCO₃-KCl（本研究）	30	72.6	10次（7%）

Fig.10 CO2-TPD curves for CaCO3-XCl

Fig.11 In situ infrared spectrum of the adsorption process of CO2 by CaCO3-XCl

Fig.12 In situ infrared spectrum of the desorption process of CO2 by CaCO3-XCl

Fig.13 SEM image of CaCO3-KCl after adsorption of CO2

Fig.14 N2 physical adsorption-desorption curves and BJH particle size distribution for CaCO3-XCl after cycling for 10 times

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Preparation of porous calcium carbonate by salt template method and its CO₂ adsorption characteristics

盐模板法制备多孔碳酸钙及其CO₂吸附特性研究

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