硅酸盐学报

低钙熟料体系中γ-C₂S与β-C₂S的共生调控及碳化机理

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张云子 ¹ , 王亚丽 ¹ , 裴天蕊 ¹ , 郑永超 ² , 赵思雪 ²

硅酸盐学报 | 研究论文 2025,53(5): 1225-1235

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硅酸盐学报 |研究论文 2025 , 53 (5) : 1225 -1235

低钙熟料体系中γ-C₂S与β-C₂S的共生调控及碳化机理

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张云子¹, 王亚丽¹, 裴天蕊¹, 郑永超², 赵思雪²

作者信息

^1．北京工业大学材料科学与工程学院，北京 100124

^2．北京建筑材料科学研究总院有限公司固废资源化利用与节能建材国家重点实验室，北京 100041

通讯作者:

王亚丽（1978—），女，博士，教授；

郑永超（1978—），男，博士，教授级高级工程师。

作者简介:

张云子（1998—），女，硕士研究生。

Symbiotic Regulation and Carbonization Mechanism of γ-C₂S and β-C₂S in Low-calcium Clinker System

Yunzi ZHANG¹, Yali WANG¹, Tianrui PEI¹, Yongchao ZHENG², Sixue ZHAO²

Affiliations

^1.School of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China

^2.State Key Laboratory of Solid Waste Reuse for Building Materials, Beijing Building Materials Academy of Science Research, Beijing 100041, China

Corresponding Author:

WANG Yali (1978-), female, Ph.D., Professor. E-mail: wangyali1978@bjut.edu.cn;

ZHENG Yongchao (1978-), male, Ph.D., Professorate Senior Engineer. anton@163.com

ZHANG Yunzi (1998-), female, Master candidate. E-mail: 18741708103@163.com

出版时间: 2025-05-20 doi: 10.14062/j.issn.0454-5648.20240689

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摘要

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为解决普通硅酸盐水泥在生产中存在的高能耗、高排放等问题，利用具有碳化活性的低钙型硅酸钙矿物（CS、C₂S与C₃S₂）替代钙含量高的C₃S矿物，不仅能够减少水泥生产中的碳排放，还能够封存CO₂。研究发现，在γ-C₂S低钙体系中掺入β-C₂S能够大幅度提升体系的力学性能。但如何一步烧成最优晶型比例的C₂S矿物，实现γ-C₂S和β-C₂S在体系内的共生成为难点。本工作使用石灰石和砂岩，通过调控煅烧温度，得到了不同比例的γ-C₂S和β-C₂S的低钙水泥熟料，采用热重、X射线衍射、pH值、电导率等测试手段对低钙水泥熟料碳化硬化机理进行了分析。结果表明：γ-C₂S/β-C₂S摩尔比例在0.19~2.63之间，随着γ-C₂S/β-C₂S比例的降低，低钙水泥熟料碳化24 h的抗压强度逐渐增加，当煅烧温度为1340 ℃，γ-C₂S/β-C₂S为0.19时，体系抗压强度可达163.32 MPa。γ-C₂S和β-C₂S存在协同碳化作用，γ-C₂S在碳化过程中放出的热量，促使β-C₂S更易溶解出Ca²⁺，促进β-C₂S碳化反应的进行，β-C₂S矿物含量较高，体系碳化后可以观察到结晶良好的方解石型碳酸钙，呈现堆叠致密的形貌。

关键词

碳排放 / 低钙熟料 / 硅酸二钙 / 碳化反应

Abstract

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Introduction

Carbon emissions in the construction industry are increasing now. Against the backdrop of environmental factors and low-carbon economy, the research on reducing carbon emission in cement industry has garnered widespread attention. During the cement production procedure, the decomposition of carbonates during the calcination of raw materials is the main source of CO₂ emissions. Therefore, reducing the calcium content in cement clinker is expexted to significantly reduce the carbon emissions, thereby achieving energy conservation and emission reduction in the industry. Unlike the C₃S mineral in ordinary Portland cement clinker, CS, C₃S₂, and γ-C₂S are three types of low calcium silicate minerals, but they are all non hydraulic minerals that cannot obtain a certain mechanical strength through traditional cement hydration. Former research revealed that the carbonation activity is higher than the hydration activity of above three low calcium minerals, and cement products can be prepared through carbonation curing.

Methods

To solve the problems of high energy consumption and high CO₂ emissions in the production of ordinary Portland cement, low calcium silicate minerals (CS, C₂S, and C₃S₂) with carbonation activity are used to replace C₃S minerals. The strategy could not only reduce carbon emissions in cement production, but also enhance utilization of carbon. Research has found that incorporating β-C₂S into the low calcium system of γ-C₂S can significantly enhance the mechanical properties of the system. In most reported research work, the single minerals are often blended after firing, and then the carbonization properties of the mixed minerals are studied. How to burn the C₂S minerals with the optimal crystal ratio in one step and to achieve the symbiosis of γ-C₂S and β-C₂S in the system remains a challenge. This work focuses on C₂S minerals. By changing the calcination temperature, C₂S minerals with different crystal ratios are treated in one step, and the relative content of γ-C₂S and β-C₂S in low calcium cement clinker is regulated. The symbiotic mechanism of the two and the influence of different mineral contents of β-C₂S and γ-C₂S on the carbonization performance of the material are studied. The carbonization products and mechanisms are explored, providing a theoretical basis for the application of low calcium fixed carbon cement in carbonization and new ideas for the carbonization research of C₂S minerals. which has certain guiding significance for energy conservation and emission reduction in the cement industry.

Results and discussion

This work used limestone and sandstone to obtain low calcium cement clinker with different proportions of γ-C₂S and β-C₂S by adjusting the calcination temperature. The carbonization and hardening mechanism of low calcium cement clinker was analyzed using thermogravimetric analysis, X-ray diffraction, pH value, conductivity and other testing methods. The results showed that the molar ratio of γ-C₂S/β-C₂S was between 0.19 and 2.63. As the ratio of γ-C₂S/β-C₂S decreased, the compressive strength of low calcium cement clinker after 24 hours of carbonization gradually increased. When the calcination temperature was 1340 ℃ and the ratio of γ-C₂S/β-C₂S was 0.19, the compressive strength of the system reached 163.32 MPa. The change in CO₂ absorption of the sample is related to the carbonation activity of calcium silicate. The early carbonization reaction of the experimental group, mainly composed of γ-C₂S minerals, is severe. There is a phenomenon of incomplete reaction in the test block. The experimental group mainly composed of β-C₂S minerals has a longer duration of exothermic reaction, which is more conducive to the progress of carbonization reaction. Among them, the heat released by γ-C₂S during the carbonization process promotes the easier dissolution of Ca²⁺ from β-C₂S, facilitating the carbonization reaction of β-C₂S. The addition of a small amount of γ-C₂S (i.e. 8.13%) has a positive effect on the carbonization degree and strength of β-C₂S. In addition, the dissolution of β-C₂S leads to a gradual increase in the pH value of the suspension, changing the liquid phase environment and accelerating the dissolution rate of γ-C₂S in water under alkaline conditions. The excellent compressive strength of the sample is attributed to its high degree of carbonization and dense microstructure. The higher the content of β-C₂S minerals (γ-C₂S/β-C₂S ratio=0.19), the better crystallized calcite type calcium carbonate can be observed after carbonization, presenting a stacked and dense morphology. The samples mainly composed of γ-C₂S minerals have weak particle bonding and loose structure after carbonization, showing amorphous calcium carbonate with many pores.

Conclusions

Therefore, it can be concluded that the synergistic carbonization of γ-C₂S and β-C₂S mainly exists in two processes: the dissolution process before CO₂ is introduced, and the carbonization reaction process after CO₂ is introduced. Due to the action of water, β-C₂S preferentially dissolves Ca²⁺, changing the liquid-phase environment around γ-C₂S particles and promoting Ca²⁺ dissolution. After the introduction of CO₂, the carbonization reaction of γ-C₂S becomes more intense, releasing a large amount of heat that accelerates the dissolution of β-C₂S minerals and promotes their carbonization reaction. The final carbonized product is mainly composed of stacked calcite, with a small amount of high polymer silica gel interspersed to bond the calcite. Therefore, the high content of β-C₂S carbonized product shows a more tightly aggregation of particles and thus better performance.

Key words

carbon emission / low-calcium clinker / dicalcium silicate / carbonization reaction

引用本文

张云子, 王亚丽, 裴天蕊, 郑永超, 赵思雪. 低钙熟料体系中γ-C₂S与β-C₂S的共生调控及碳化机理. 硅酸盐学报, 2025 , 53 (5) : 1225 -1235 . DOI: 10.14062/j.issn.0454-5648.20240689

Yunzi ZHANG, Yali WANG, Tianrui PEI, Yongchao ZHENG, Sixue ZHAO. Symbiotic Regulation and Carbonization Mechanism of γ-C₂S and β-C₂S in Low-calcium Clinker System[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (5) : 1225 -1235 . DOI: 10.14062/j.issn.0454-5648.20240689

基金

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国家重点研发计划(2023YFB4204302)
北京金隅“低钙固碳胶凝材料技术开发”项目

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2025年第53卷第5期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240689

接收时间：2024-10-30
首发时间：2026-10-22
出版时间：2025-05-20

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收稿日期：2024-10-30
修回日期：2024-12-30

基金

国家重点研发计划(2023YFB4204302)

北京金隅“低钙固碳胶凝材料技术开发”项目

作者信息

^1．北京工业大学材料科学与工程学院，北京 100124

^2．北京建筑材料科学研究总院有限公司固废资源化利用与节能建材国家重点实验室，北京 100041

通讯作者:

王亚丽（1978—），女，博士，教授；

郑永超（1978—），男，博士，教授级高级工程师。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240689

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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