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Research Article Issue
Symbiotic Regulation and Carbonization Mechanism of γ-C2S and β-C2S in Low-calcium Clinker System
Journal of the Chinese Ceramic Society 2025, 53(5): 1225-1235
Published: 26 March 2025
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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.

Review Issue
Research Progress on CO2 Capture in Cement Kiln Flue Gas and Modification of Absorption Efficiency of Calcium Carbide Slag
Journal of the Chinese Ceramic Society 2025, 53(5): 1258-1268
Published: 09 January 2025
Abstract PDF (3.7 MB) Collect
Downloads:5

Carbon dioxide emissions from cement kiln flue gas constitute a significant contributor to global climate change and environmental pollution. As global emission reduction targets progress, research and application of carbon capture, utilization, and storage (CCUS) technologies have increasingly become critical strategies for mitigating CO2 emissions. Among these technologies, the calcium cycle method demonstrates substantial potential due to its low cost, high efficiency in CO2 trapping, and broad applicability, particularly in the context of cement kiln flue gas. However, traditional calcium-based materials, such as limestone, face challenges including high precalcination temperatures and resource wastage, highlighting the need for more efficient and sustainable alternatives.

Calcium carbide slag, an industrial by-product, has shown significant promise as a material for the calcium cycle method. It contains a high proportion of reactive CaO, along with inert components such as alumina and magnesium oxide. These inert components enhance resistance to sintering after preburning. However, repeated use of calcium carbide slag leads to pore structure collapse, particle agglomeration, and sintering, severely diminishing its adsorption performance and posing a significant barrier to practical application.

To address these challenges, various modification techniques have been explored to improve the absorption efficiency and sintering properties of calcium carbide slag, as well as to mitigate the impact of SO2 and NOx in flue gas on CO2 absorption.

Organic acid modification has been identified as an effective strategy to enhance the adsorption performance of calcium carbide slag. Through reactions with calcium hydroxide to form organic calcium salts, pyrolysis at high temperatures releases small molecules that disrupt the original structure of the slag. This process increases porosity, specific surface area, and CO2 adsorption capacity. Different organic acids, due to their distinct molecular structures, yield variations in the molecular weight of organic calcium salts and the types and quantities of small molecules released during pyrolysis. Consequently, modifying calcium carbide slag with specific organic acids allows tailoring of its pore structure to enhance CO2 adsorption performance.

Doping modification technology is another effective approach. By incorporating various substances into the slag, the properties of calcium carbide slag can be optimized through different chemical reaction mechanisms. Inert materials serve as structural frameworks, inhibiting CaO grain migration and growth to improve anti-sintering performance. Doping with oxygen-deficient materials facilitates CO2 diffusion and O2- migration, while potassium and sodium salts increase defect concentrations in the CaCO3 product layer, enabling more efficient Ca2+ migration and enhanced CO2 absorption.

Hydration processes also play a critical role in influencing sintering. While CaCO3 typically decomposes at high temperatures, introducing water vapor during calcination reduces the partial pressure of CO2, promoting its conversion to CaO. Water vapor also shortens decomposition residence time and slows sintering, delaying sintering deactivation and improving stability. By optimizing calcination temperatures and water vapor concentrations, the CO2 adsorption performance and stability of calcium carbide slag can be enhanced over multiple cycles.

In the context of cement kiln flue gas treatment, SO2 and NOx pose additional challenges to the CO2 trapping performance of calcium carbide slag. SO2, being strongly acidic, preferentially reacts with CaO to form dense CaSO4 layers, which accumulate over cycles, diminishing adsorbent activity. Research suggests that specific modification methods or adjustments in the absorption sequence (e.g., absorbing CO2 before SO2) can mitigate these effects. Regarding NOx, calcium carbide slag inherently lacks reductive properties and cannot remove NOx through traditional calcium cycle methods. Doping with reducing substances, such as copper, iron, and other metal oxides, can enable NOx reduction by promoting reactions that convert NOx into harmless nitrogen and oxygen.

Summary and prospects

The future of calcium carbide slag modification technology is expected to move towards systematic and refined strategies. These strategies can leverage the synergistic effects of multiple modification techniques to optimize performance across different reaction stages. As research progresses, the multifaceted applications of calcium carbide slag will gain increasing recognition. Beyond its role in CO2 capture, it holds significant potential for processes such as desulfurization and nitrogen removal.

From an environmental perspective, utilizing calcium carbide slag addresses resource wastage while aiding the cement industry in achieving a green transformation by reducing greenhouse gases and pollutants such as CO2, SO2, and NOx. Continuous innovation in modification technology will ensure that calcium carbide slag not only plays a pivotal role in CO2 capture but also in mitigating pollutants, contributing to the attainment of global emission reduction goals. The enhanced versatility and cyclic stability of modified calcium carbide slag will further support the green transition of the cement industry and other high-emission sectors, contributing to efforts toward a sustainable future.

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