低钙高镁石灰石制备固碳熟料及其碳酸化硬化机理

doi:10.16552/j.cnki.issn1001-1625.2025.0104

硅酸盐通报 ›› 2025, Vol. 44 ›› Issue (8): 2762-2770.DOI: 10.16552/j.cnki.issn1001-1625.2025.0104

低钙高镁石灰石制备固碳熟料及其碳酸化硬化机理

朱建平¹, 曹佳楠¹, 王祚麟¹, 李根深¹, 刘松辉¹, 郑波², 冯春花¹

1.河南理工大学材料科学与工程学院,焦作 454003;
2.焦作千业水泥有限责任公司,焦作 454100

收稿日期:2025-01-30 修订日期:2025-03-14 出版日期:2025-08-15 发布日期:2025-08-22
通信作者: 冯春花,副教授。E-mail:fengchunhua@hpu.edu.cn
作者简介:朱建平(1978—),男,教授。主要从事绿色建材方面的研究。E-mail:jianpingzhu@hpu.edu.cn
基金资助:
全国建材行业重大科技攻关“揭榜挂帅”项目(2021JBGS03-11)

Preparation of Carbonation-Bonded Clinker from Low-Calcium High-Magnesium Limestone and Its Carbonation-Hardening Mechanism

ZHU Jianping¹, CAO Jianan¹, WANG Zuolin¹, LI Genshen¹, LIU Songhui¹, ZHENG Bo², FENG Chunhua¹

1. School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, China;
2. Jiaozao Qianye Cement Limited Liability Company, Jiaozuo 454100, China

Received:2025-01-30 Revised:2025-03-14 Published:2025-08-15 Online:2025-08-22

摘要/Abstract

摘要： 为了应对传统硅酸盐水泥生产面临的原料限制和碳排放问题,采用低钙高镁石灰石(MgO质量分数大于5%)和砂岩为原料,制备了一种新型低钙高镁水泥熟料。该熟料以白硅钙石(Ca₇MgSi₄O₁₆,C₇MS₄)、斜硅钙石(β-Ca₂SiO₄,β-C₂S)、氧化镁(MgO)和镁硅钙石(Ca₃MgSi₂O₈,C₃MS₂)为主要矿物,通过原料替代减少石灰石用量,并利用镁质矿物的高反应活性,实现二氧化碳矿化养护混凝土技术。研究结果显示,该熟料体系在1 220~1 260 ℃下形成,经煅烧、粉磨成型后,在CO₂纯度为99.9%(体积分数)、压强为0.3 MPa的条件下碳酸化24 h,抗压强度可达90.2 MPa,固碳率高达9.22%。该技术为水泥工业提供了“源头减碳-过程固碳”的双重减排方案,不仅降低了石灰石用量,还实现了CO₂的有效封存,为水泥行业的绿色低碳转型提供了新的技术路径。

关键词: 低钙硅酸盐胶凝材料, 碳酸化养护, 胶凝材料组成, 烧成制度, 高镁石灰石, 力学性能

Abstract: To tackle the issues of raw material constraints and carbon emissions in traditional Portland cement production, a new type of low-calcium and high-magnesium cement clinker was prepared using low-calcium and high-magnesium limestone (MgO mass fraction greater than 5%) and sandstone as raw materials. The main minerals of this clinker arebredigite (Ca₇MgSi₄O₁₆ , C₇MS₄), larnite (β-Ca₂SiO₄, β-C₂S),periclase (MgO) and merwinite (Ca₃MgSi₂O₈, C₃MS₂). By substituting raw materials, the consumption of limestone is reduced, and the high reactivity of magnesium minerals is utilized to realize the CO₂ mineralization curing technology for concrete. The research results show that this clinker system is formed at 1 220~1 260 ℃. After calcination, grinding and molding, and carbonation for 24 h under the conditions of a CO₂ purity of 99.9% (volume fraction) and a pressure of 0.3 MPa, the compressive strength can reach 90.2 MPa, and the carbon sequestration rate is as high as 9.22%. This technology offers a dual-emission-reduction solution of “source carbon reduction-process carbon sequestration” for the cement industry. It not only cuts down the limestone usage but also effectively sequesters CO₂, providing a new technological route for the green and low-carbon transformation of the cement industry.

Key words: low-calcium silicate cementitious material, carbonation curing, composition of cementitious materials, sintering system, high-magnesium limestone, mechanical property

中图分类号:

TU526

朱建平, 曹佳楠, 王祚麟, 李根深, 刘松辉, 郑波, 冯春花. 低钙高镁石灰石制备固碳熟料及其碳酸化硬化机理[J]. 硅酸盐通报, 2025, 44(8): 2762-2770.

ZHU Jianping, CAO Jianan, WANG Zuolin, LI Genshen, LIU Songhui, ZHENG Bo, FENG Chunhua. Preparation of Carbonation-Bonded Clinker from Low-Calcium High-Magnesium Limestone and Its Carbonation-Hardening Mechanism[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2025, 44(8): 2762-2770.

参考文献

[1] MADDALENA R, ROBERTS J J, HAMILTON A. Can Portland cement be replaced by low-carbon alternative materials?A study on the thermal properties and carbon emissions of innovative cements[J]. Journal of Cleaner Production, 2018, 186: 933-942.
[2] HAWKINS P, TENNIS P, DETWILER R. The use of limestone in Portland cement: a state-of-the-art review[M]. Skokie, IL, USA: Portland Cement Association, 2003.
[3] HOU G H, CHEN J N, LU B, et al. Composition design and pilot study of an advanced energy-saving and low-carbon rankinite clinker[J]. Cement and Concrete Research, 2020, 127: 105926.
[4] DE SOUZA F, BRAGANÇA S R. Thermogravimetric analysis of limestones with different contents of MgO and microstructural characterization in oxy-combustion[J]. Thermochimica Acta, 2013, 561: 19-25.
[5] LI X R, HUANG H, XU J, et al. Statistical research on phase formation and modification of alite polymorphs in cement clinker with SO₃ and MgO[J]. Construction and Building Materials, 2012, 37: 548-555.
[6] MO L W, DENG M, TANG M S, et al. MgO expansive cement and concrete in China: past, present and future[J]. Cement and Concrete Research, 2014, 57: 1-12.
[7] ZHANG W S, LUAN Z B, REN X H, et al. Influence of alumina modulus on formation of high-magnesium clinker and morphological evolution of MgO[J]. Cement and Concrete Research, 2022, 162: 106986.
[8] TANG Y J, ZHAO L, LI B, et al. Controlling the soundness of Portland cement clinker synthesized with solid wastes based on phase transition of MgNiO₂[J]. Cement and Concrete Research, 2022, 157: 106832.
[9] JANG J G, KIM G M, KIM H J, et al. Review on recent advances in CO₂ utilization and sequestration technologies in cement-based materials[J]. Construction and Building Materials, 2016, 127: 762-773.
[10] LIU S H, LI D L, ZHANG X Y, et al. Utilization of magnesian limestone in carbonatable binders: reaction mechanisms and performance analysis[J]. Construction and Building Materials, 2025, 469: 140497.
[11] BODOR M, SANTOS R M, KRISKOVA L, et al. Susceptibility of mineral phases of steel slags towards carbonation: mineralogical, morphological and chemical assessment[J]. European Journal of Mineralogy, 2013, 25(4): 533-549.
[12] 徐信文, 严彬. 高镁石灰石煅烧优质熟料的生产应用[J]. 中国水泥, 2024(增刊2): 131-134.
XU X W, YAN B. Production and application of calcining high quality clinker with high magnesium limestone[J]. China Cement, 2024(supplement 2): 131-134 (in Chinese).
[13] ZHU J P, MA D, LIU S H, et al. The influence of nano-SiO₂ on the carbonation properties of low calcium CO₂ sequestration binder and its mechanism[J]. Construction and Building Materials, 2024, 416: 135124.
[14] ZHAO R Q, ZHANG L, FAN G X, et al. Probing the exact form and doping preference of magnesium in ordinary Portland cement clinker phases: a study from experiments and DFT simulations[J]. Cement and Concrete Research, 2021, 144: 106420.
[15] BAO X J, HE M Y, ZHANG Z G, et al. Crystal structure and some thermodynamic properties of Ca₇MgSi₄O₁₆-bredigite[J]. Crystals, 2021, 11(1): 14.
[16] LIU S H, RONG P J, ZHANG S S, et al. Enhancing CO₂-cured cementitious binder with Mg-doped γ-C₂S from high-Mg limestone[J]. Developments in the Built Environment, 2024, 17: 100312.
[17] MIRHADI S M, TAVANGARIAN F, EMADI R. Synthesis, characterization and formation mechanism of single-phase nanostructure bredigite powder[J]. Materials Science and Engineering: C, 2012, 32(2): 133-139.
[18] ZHAO S X, LIU Z C, WANG F Z, et al. Elucidating factors on the strength of carbonated compacts: insights from the carbonation of γ-C₂S, β-C₂S and C₃S[J]. Cement and Concrete Composites, 2025, 155: 105806.
[19] JIANG Y, LI L, LU J X, et al. Enhancing the microstructure and surface texture of recycled concrete fine aggregate via magnesium-modified carbonation[J]. Cement and Concrete Research, 2022, 162: 106967.
[20] HOLLINGBERY L A, HULL T R. The thermal decomposition of huntite and hydromagnesite: a review[J]. Thermochimica Acta, 2010, 509(1/2): 1-11.
[21] HAY R, PENG B, CELIK K. Filler effects of CaCO₃ polymorphs derived from limestone and seashell on hydration and carbonation of reactive magnesium oxide (MgO) cement (RMC)[J]. Cement and Concrete Research, 2023, 164: 107040.
[22] WANG D, CHANG J, ANSARI W S. The effects of carbonation and hydration on the mineralogy and microstructure of basic oxygen furnace slag products[J]. Journal of CO₂ Utilization, 2019, 34: 87-98.
[23] DUNG N T, UNLUER C. Improving the performance of reactive MgO cement-based concrete mixes[J]. Construction and Building Materials, 2016, 126: 747-758.
[24] HUO J H, PENG Z G, YE Z B, et al. Characterising the hydration process of cement slurry system based on low-field NMR[J]. Advances in Cement Research, 2020, 32(1): 12-19.
[25] WENK H, HU M, FRISIA S. Partially disordered dolomite; microstructural characterization of Abu Dhabi sabkha carbonates[J]. The American mineralogist, 1993, 78(7/8): 769-774.

低钙高镁石灰石制备固碳熟料及其碳酸化硬化机理

Preparation of Carbonation-Bonded Clinker from Low-Calcium High-Magnesium Limestone and Its Carbonation-Hardening Mechanism

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