盐模板法制备多孔碳酸钙及其CO2吸附特性研究

doi:10.11949/0438-1157.20250285

化工学报 ›› 2025, Vol. 76 ›› Issue (11): 6086-6099.DOI: 10.11949/0438-1157.20250285

• 材料化学工程与纳米技术 • 上一篇下一篇

盐模板法制备多孔碳酸钙及其CO₂吸附特性研究

石美玉¹(), 赵波琛¹, 束远¹, 牛强²(), 张鹏飞¹^,³()

^1.宁夏大学化学化工学院省部共建煤炭高效利用与绿色化工国家重点实验室，宁夏银川 750021
^2.内蒙古鄂尔多斯电力冶金集团股份有限公司国家企业技术中心，内蒙古鄂尔多斯 016064
^3.上海交通大学化学化工学院，上海 200240

收稿日期:2025-03-24 修回日期:2025-05-08 出版日期:2025-11-25 发布日期:2025-12-19
通讯作者: 牛强,张鹏飞
作者简介:石美玉（1996—），女，博士研究生，Smy1464632131@163.com
基金资助:
内蒙古自治区重点研发计划(2021ZD0042);内蒙古自治区重点研发计划(2021EEDSCXSFQZD006);内蒙古自治区重点研发计划(2021GG0350);鄂尔多斯市重点研发计划项目(2121HZ231-8)

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

Meiyu SHI¹(), Bochen ZHAO¹, Yuan SHU¹, Qiang NIU²(), Pengfei ZHANG¹^,³()

^1.State Key Laboratory of High-efffciency Utilization of Coal and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China
^2.Inner Mongolia Erdos Power and Metallurgy Group Co. , Ltd. , Ordos 016064, Inner Mongolia, China
^3.School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Received:2025-03-24 Revised:2025-05-08 Online:2025-11-25 Published:2025-12-19
Contact: Qiang NIU, Pengfei ZHANG

摘要/Abstract

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

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

中图分类号:

TQ 132.3

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.

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.

图/表 16

图1 合成CaCO3各步骤中间产物的XRD谱图

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

图2 不同阶段样品的SEM图像

Fig.2 SEM images of samples at different stages

图3 多孔CaCO3-XCl的SEM图像

Fig.3 SEM images of porous CaCO3-XCl

表1 CaCO3-XCl的比表面积、孔容及孔径

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

图4 CaCO3-XCl的N2物理吸附-脱附曲线和BJH粒径分布

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

图5 以KCl为模板剂制备多孔CaCO3的TEM图像

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

图6 CaCO3-XCl的红外光谱图

Fig.6 Infrared spectrum of CaCO3-XCl

图7 CaCO3-XCl的拉曼光谱图

Fig.7 Raman spectra of CaCO3-XCl

图8 不同模板剂制备的CaCO3的CO2静态吸附性能

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

图9 CaCO3-XCl的CO2静态吸附性能和循环吸附

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

表2 本研究中的吸附剂与同类典型Ca基吸附剂的循环稳定性比较

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%）

图10 CaCO3-XCl的CO2-TPD曲线

Fig.10 CO2-TPD curves for CaCO3-XCl

图11 CaCO3-XCl对CO2吸附过程的原位红外光谱图

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

图12 CaCO3-XCl对CO2脱附过程的原位红外光谱图

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

图13 CaCO3-KCl吸附CO2后的SEM图像

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

图14 循环10次后CaCO3-XCl的N2物理吸脱附曲线和BJH粒径分布

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

参考文献 42

[1]	虎雅荣, 李三秀, 彭娟. 海参状Cu₂O/Cu@N-C的制备及电化学还原CO₂制甲酸盐[J]. 宁夏大学学报(自然科学版), 2024, 45(4): 379-388.
	Hu Y R, Li S X, Peng J. Preparation of sea cucumber-like Cu₂O/Cu@N-C and electrochemical reduction of CO₂ to produce formate[J]. Journal of Ningxia University (Natural Science Edition), 2024, 45(4): 379-388.
[2]	Zhao C B, Wang L M, Huang L, et al. Recent advances in intermediate-temperature CO₂capture: materials, technologies and applications[J]. Journal of Energy Chemistry, 2024, 90: 435-452.
[3]	赵俊德, 周爱国, 陈彦霖, 等. 吸附法CO₂直接空气捕集技术能耗现状[J]. 化工学报, 2025, 76(4): 1375-1390.
	Zhao J D, Zhou A G, Chen Y L, et al. Energy consumption of adsorption CO₂ direct air capture[J]. China Industrial Economics, 2025, 76(4): 1375-1390.
[4]	王炳杰, 解强, 沙雨桐, 等. CO₂吸附用竹基活性炭制备研究进展[J]. 新型炭材料, 2025, 40(2): 317-322.
	Wang B J, Xie Q, Sha Y T, et al. Research progress on the preparation of bamboo-based activated carbon for CO₂ adsorption[J]. New Carbon Materials, 2025, 40(2): 1-17.
[5]	Lu W, Li J, Qi G S, et al. Preparation and properties of zeolite-fly ash-slag composite porous materials: CO₂ adsorption performance and mechanical property[J]. Environmental Science and Pollution Research, 2023, 30(10): 27303-27314.
[6]	杜盛郁, 牛强, 张鹏飞. 反应性挤出技术制备碳基乙炔氢氯化催化剂[J]. 宁夏大学学报(自然科学版), 2024, 45(3): 273-281.
	Du S Y, Niu Q, Zhang P F. Synthesis of carbon-based catalysts for acetylene hydrochlorination using reactive extrusion technology[J]. Journal of Ningxia University (Natural Science Edition), 2024, 45(3): 273-281.
[7]	王恩民, 李文翠, 雷成, 等. 碱式碳酸镁催化酚醛聚合制备多孔炭及其CO₂吸附性能[J]. 化工学报, 2015, 66(7): 2565-2572.
	Wang E M, Li W C, Lei C, et al. Synthesis of porous carbon through polymerization catalyzed by basic magnesium carbonate and their CO₂ adsorption performance[J]. CIESC Journal, 2015, 66(7): 2565-2572.
[8]	Boyjoo Y, Merigot, Lamonier J F, et al. Synthesis of CaCO₃@C yolk-shell particles for CO₂ adsorption[J]. RSC Advances, 2015, 5(32): 24872-24876.
[9]	冯嘉琪. 多壳层碳酸钙空心微球吸附剂的制备及其CO₂吸附性能研究[D]. 天津: 天津大学, 2017.
	Feng J Q. Preparation and CO₂ adsorption capacity of multi-shelled hollow CaCO₃ microspheres[D]. Tianjin: Tianjin University, 2017.
[10]	师琦, 吴素芳. 沉淀法SiO₂包覆纳米CaCO₃吸附剂性能[J]. 化工学报, 2009, 60(2): 507-513.
	Shi Q, Wu S F. Properties of SiO₂coated nano SiO₂/CaCO₃ sorbents by precipitation method[J]. Journal of the Chemical Industry and Engineering Society of China, 2009, 60(2): 507-513.
[11]	Feng J Q, Guo H X, Wang S P, et al. Fabrication of multi-shelled hollow Mg-modified CaCO₃ microspheres and their improved CO₂ adsorption performance[J]. Chemical Engineering Journal, 2017, 321: 401-411.
[12]	Li S, Jiang T, Xu Z H, et al. The Mn-promoted double-shelled CaCO₃ hollow microspheres as high efficient CO₂ adsorbents[J]. Chemical Engineering Journal, 2019, 372: 53-64.
[13]	Liu X, Zhang J, Liu K, et al. Regulation of the pore structure of carbon nanosheets based electrocatalyst for efficient polysulfides phase conversions[J]. Journal of Materials Science & Technology, 2024, 171: 37-46.
[14]	Shi J S, Xu J G, Cui H M, et al. NaCl template synthesis of N-doped porous carbon from magnesium gluconate for efficient CO₂ adsorption[J]. Separation and Purification Technology, 2025, 355: 129756.
[15]	Dong H, Fu X L, Wang J, et al. In-situ construction of porous Si@C composites with LiCl template to provide silicon anode expansion buffer[J]. Carbon, 2021, 173: 687-695.
[16]	Wu M, Yan D J, Tang X N, et al. Synthesis of potassium-modified graphitic carbon nitride with high photocatalytic activity for hydrogen evolution[J]. ChemSusChem, 2014, 7(9): 2654-2658.
[17]	Qiu D, Cao T F, Zhang J, et al. Precise carbon structure control by salt template for high performance sodium-ion storage[J]. Journal of Energy Chemistry, 2019, 31: 101-106.
[18]	Cao Y H, Wang X M, Gu Z R, et al. Potassium chloride templated carbon preparation for supercapacitor[J]. Journal of Power Sources, 2018, 384: 360-366.
[19]	Durmus F C, Jordá J M M. Silver foams with hierarchical porous structures: from manufacturing to antibacterial activity[J]. ACS Applied Materials & Interfaces, 2021, 13(30): 35865-35877.
[20]	Huang M Z, Zeng W Y, Zhu Z W. Facile synthesis of porous Mo₂C/C composites by using luffa sponge-derived carbon template in molten salt media[J]. Royal Society Open Science, 2019, 6(6). 190547-190552.
[21]	Song P, Li C C, Zhao N M, et al. Molten salt-confined pyrolysis towards heteroatom-doped porous carbon nanosheets for high-energy-density Zn-ion hybrid supercapacitors[J]. Journal of Colloid and Interface Science, 2023, 633: 362-373.
[22]	Rehman A, Park S J. Environmental remediation by microporous carbon: an efficient contender for CO₂ and methylene blue adsorption[J]. Journal of CO₂ Utilization, 2019, 34: 656-667.
[23]	Chui S Y, Kao C Y, Huang T T, et al. Microalgal biomass production and on-site bioremediation of carbon dioxide, nitrogen oxide and sulfur dioxide from flue gas using Chlorella sp. cultures[J]. Bioresource Technology, 2011, 102(19): 9135-9142.
[24]	Liu C B, Wang Y T, Zhang B. Synthesis of ammonia via an electroreduction removal of NO from exhausted gas: an upgrading to N₂ fixation[J]. Science China Chemistry, 2020, 63(9): 1173-1174.
[25]	Shu Y, Liu Q, Shi M, et al. Surfactant-free synthesis of crystalline mesoporous metal oxides by a seeds/NaCl-mediated growth strategy[J]. Advanced Science, 2024, 11(1): 2304533-230462.
[26]	Sotelo A, Rasekh S, Torres M A, et al. Effect of synthesis methods on the Ca₃Co₄O₉ thermoelectric ceramic performances[J]. Journal of Solid State Chemistry, 2015, 221: 247-254.
[27]	Nahar A, Sahadat Hossain M, Akbor M A, et al. Evaluation of anti-microbial activity of biotite and biotite composite based on crystallographic parameters: estimation of crystallite size employing X-ray diffraction data[J]. Results in Engineering, 2024, 23: 102595.
[28]	Cao Z, An Y T, Wang X L, et al. Characterization of corrosion behavior of CLF-1 in liquid lithium using calibration-free laser-induced breakdown spectroscopy in depth profile analysis[J]. Materials, 2020, 13(1): 240-252.
[29]	Chen Y y, Hu Z P, Xu Y F, et al. Microstructure evolution and interface structure of Al-40 wt% Si composites produced by high-energy ball milling[J]. Journal of Materials Science & Technology, 2019, 35(4): 512-519.
[30]	Mähler J, Persson I. A study of the hydration of the alkali metal ions in aqueous solution[J]. Inorganic Chemistry, 2012, 51(1): 425-438.
[31]	Chen L, Shi G S, Shen J, et al. Ion sieving in graphene oxide membranes via cationic control of interlayer spacing[J]. Nature, 2017, 550(7676): 380-383.
[32]	Horikawa T, Muguruma T, Do D D, et al. Scanning curves of water adsorption on graphitized thermal carbon black and ordered mesoporous carbon[J]. Carbon, 2015, 95: 137-143.
[33]	Williams S F, Wan H, Chittock J, et al. Characterization of skin barrier defects using infrared spectroscopy in patients with atopic dermatitis[J]. Clinical and Experimental Dermatology, 2024, 49(5): 466-477.
[34]	Shi B N, Zhang L F, Yang Z D, et al. Photothermal conversion-enabled temperature modulation for the growth of complex polymorphic architectures of calcium carbonate[J]. Journal of Materials Chemistry A, 2024, 12(25): 15090-15098.
[35]	Sun H J, Meng X X, Luo C F, et al. Quantifying crystallinity in poly(p-phenylene terephthalamide) by Raman spectroscopy[J]. Macromolecules, 2024, 57(15): 7390-7397.
[36]	Marshall C P, Stockdale G, Carr C A. Raman spectroscopy of geological varieties of hematite of varying crystallinity and morphology[J]. Journal of Raman Spectroscopy, 2025, 56(7): 590-597.
[37]	Wang P P, Shi M Y, Shu Y, et al. Porous CaCO₃ fabricated by Ca-containing solid wastes for effective CO₂ adsorption[J]. Journal of Environmental Chemical Engineering, 2025, 13(2): 115815.
[38]	司康乐, 匡盛铎, 罗长新, 等. 鸡蛋壳源Ca基吸附剂制备及其CO₂吸附性能的研究[J]. 电力科技与环保, 2024, 40(5): 513-523.
	Si K L, Kuang S D, Luo C X, et al. Preparation of eggshell-derived calcium-based adsorbent and its CO₂ adsorption performance[J]. Electric Power Technology and Environmental Protection, 2024, 40(5): 513-523.
[39]	Teixeira P, Correia P, Pinheiro C I C. CO₂ capture by CaCO₃-MgO and CeO₂-MgO sorbents promoted by ternary alkali metal salts in a fixed bed reactor[J]. Chemical Engineering Science, 2024, 289: 119856.
[40]	Song J B, Qu T, Zhang J P, et al. Enhancing cyclic stability and anti-sintering capacity of CaCO₃-MgO sorbents for CO₂ capture[J]. Chemical Engineering Science, 2025, 309: 121433.
[41]	Yao S L, Zhang H H, Chen Z Z, et al. Promotion of graphitic carbon oxidation via stimulating CO₂ desorption by calcium carbonate[J]. Journal of Hazardous Materials, 2019, 363: 10-15.
[42]	Finnie K S, Cassidy D J, Bartlett J R, et al. IR spectroscopy of surface water and hydroxyl species on nanocrystalline TiO₂ films[J]. Langmuir, 2001, 17(3): 816-820.

盐模板法制备多孔碳酸钙及其CO₂吸附特性研究

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

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