脱硫石膏对铝酸钙-电石渣协同激发超硫酸盐水泥水化特性的调控机理

doi:10.16552/j.cnki.issn1001-1625.2024.0142

摘要/Abstract

摘要： 本研究旨在提高脱硫石膏的资源化利用率,探讨脱硫石膏掺量对铝酸钙-电石渣协同激发超硫酸盐水泥水化特性的影响。通过力学性能测试、水化产物分析及微观结构表征,揭示脱硫石膏对超硫酸盐水泥水化机理与性能演变的影响。结果表明,超硫酸盐水泥的抗压强度随着脱硫石膏掺量增加而持续增长,当脱硫石膏掺量增加至20%(质量分数)时,抗压强度达到最大值。在水化早期,脱硫石膏与铝酸钙迅速反应生成钙矾石。电石渣提供碱性环境,促进矿渣溶解,并加速矿渣与脱硫石膏反应生成大量钙矾石,同时,水化硅酸钙和水滑石等水化产物的形成,与上述反应协同加快了早期强度发展。在水化后期,随着脱硫石膏逐渐消耗,钙矾石生成速度下降,水化硅酸钙逐步转变为主要水化产物,持续提升基体强度。

关键词: 超硫酸盐水泥, 脱硫石膏, 力学性能, 水化热, 水化产物, 微观结构

Abstract: The purpose of this study is to improve the resource utilization rate of flue gas desulfurization gypsum, and to explore the effect of flue gas desulfurization gypsum content on the hydration characteristics of supersulfated cement co-activated with calcium aluminate and carbide slag. The effect of flue gas desulfurization gypsum on the hydration mechanism and performance evolution of supersulfate cement was revealed by mechanical property test, hydration product analysis and microstructure characterization. The results show that the compressive strength of supersulfated cement continues to increase with the increase of flue gas desulfurization gypsum content. When the flue gas desulfurization gypsum content increases to 20% (mass fraction), the compressive strength reaches the maximum value. In the early hydration stage, flue gas desulfurized gypsum reacts rapidly with calcium aluminate to form ettringite. Carbide slag provides an alkaline environment, promotes the dissolution of slag, and accelerates the reaction of slag and flue gas desulfurized gypsum to form a large amount of ettringite. At the same time, the formation of hydration products such as calcium silicate hydrate and hydrotalcite accelerates the development of early strength in coordination with the above reactions. In the later hydration, with the gradual consumption of flue gas desulfurized gypsum, the formation rate of ettringite decreases, and calcium silicate hydrate gradually transforms into the main hydration product, continuously improving the strength of matrix.

Key words: supersulfated cement, flue gas desulfurization gypsum, mechanical property, hydration heat, hydration product, microstructure

中图分类号:

TQ172

齐广政, 张强, 刘宣. 脱硫石膏对铝酸钙-电石渣协同激发超硫酸盐水泥水化特性的调控机理[J]. 硅酸盐通报, 2025, 44(6): 2250-2258.

QI Guangzheng, ZHANG Qiang, LIU Xuan. Regulation Mechanism of Flue Gas Desulfurization Gypsum on Hydration Characteristics of Supersulfated Cement Co-Activated withCalcium Aluminate and Carbide Slag[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2025, 44(6): 2250-2258.

参考文献

[1] HASANBEIGI A, PRICE L, LIN E. Emerging energy-efficiency and CO₂ emission-reduction technologies for cement and concrete production: a technical review[J]. Renewable and Sustainable Energy Reviews, 2012, 16(8): 6220-6238.
[2] GARTNER E. Industrially interesting approaches to “low-CO₂” cements[J]. Cement and Concrete Research, 2004, 34(9): 1489-1498.
[3] ANDREW R M. Global CO₂ emissions from cement production[J]. Earth System Science Data, 2019, 11(4): 1675-1710.
[4] 孙正宁, 周健, 慕儒, 等. 新型超硫酸盐水泥水化硬化机理[J]. 硅酸盐通报, 2019, 38(8): 2362-2368.
SUN Z N, ZHOU J, MU R, et al. Hydration and hardening mechanisms of newly developed supersulfated cement[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(8): 2362-2368 (in Chinese).
[5] WU Q Y, XUE Q Z, YU Z Q. Research status of super sulfate cement[J]. Journal of Cleaner Production, 2021, 294: 126228.
[6] PINTO S R, ANGULSKI DA LUZ C, MUNHOZ G S, et al. Durability of phosphogypsum-based supersulfated cement mortar against external attack by sodium and magnesium sulfate[J]. Cement and Concrete Research, 2020, 136: 106172.
[7] ABD EL AZIZ M, ABD EL ALEEM S, HEIKAL M, et al. Hydration and durability of sulphate-resisting and slag cement blends in Caron’s Lake water[J]. Cement and Concrete Research, 2005, 35(8): 1592-1600.
[8] GRUSKOVNJAK A, LOTHENBACH B, WINNEFELD F, et al. Hydration mechanisms of super sulphated slag cement[J]. Cement and Concrete Research, 2008, 38(7): 983-992.
[9] ERDEM E, HALIS Ö. The mechanical properties of supersulphated cement containing phosphogypsum[J]. Cement and Concrete Research, 1993, 23(1): 115-121.
[10] 王露, 涂拥军, 高富豪, 等. 改性磷石膏对超硫酸盐水泥水化特性的影响[J]. 材料导报, 2024, 38(14): 138-143.
WANG L, TU Y J, GAO F H, et al. Effect of modified phosphogypsum on hydration characteristics of supersulfated cement[J]. Materials Reports, 2024, 38(14): 138-143 (in Chinese).
[11] LI J S, ZHANG W, HUANG X, et al. MgO-based supersulfated cement with different industrial by-product gypsum: experiments and molecular dynamics simulation[J]. Science of the Total Environment, 2024, 941: 173756.
[12] LI B B, HOU P K, CHEN H, et al. GGBS hydration acceleration evidence in supersulfated cement by nano SiO₂[J]. Cement and Concrete Composites, 2022, 132: 104609.
[13] ZHOU Y, PENG Z C, CHEN L C, et al. The influence of two types of alkali activators on the microstructure and performance of supersulfated cement concrete: mitigating the strength and carbonation resistance[J]. Cement and Concrete Composites, 2021, 118: 103947.
[14] 王若愚, 王焕焕, 陈衡, 等. 纳米二氧化硅对超硫酸盐水泥中石膏最佳掺量的影响[J]. 硅酸盐通报, 2024, 43(3): 995-1002.
WANG R Y, WANG H H, CHEN H, et al. Effect of nano-SiO₂ on optimum gypsum content in supersulfate cement[J]. Bulletin of the Chinese Ceramic Society, 2024, 43(3): 995-1002 (in Chinese).
[15] AAKRIT I, MAITI S, JAIN N, et al. A comprehensive review of flue gas desulphurized gypsum: production, properties, and applications[J]. Construction and Building Materials, 2023, 393: 131918.
[16] NGUYEN H A, CHEN C T, CHANG T P, et al. Utilizations of preheated flue gas desulfurization gypsum and sulfate compositions to modify performances of super-sulfated cement[J]. Journal of Thermal Analysis and Calorimetry, 2023, 148(24): 13761-13773.
[17] 施惠生, 刘红岩. 脱硫石膏在矿渣水泥中的资源化利用[J]. 同济大学学报(自然科学版), 2008, 36(1): 66-70.
SHI H S, LIU H Y. Resource recovery of flue gas desulphurization gypsum in slag cement[J]. Journal of Tongji University (Natural Science), 2008, 36(1): 66-70 (in Chinese).
[18] ZHU G J, QI Z J, KOU Y P. Kinetic study on the hydration of supersulfated cements[J]. Journal of Thermal Analysis and Calorimetry, 2024, 149(11): 5285-5297.
[19] 周建伟, 程宝军, 余保英, 等. 脱硫石膏的热处理对超硫酸盐水泥性能的影响[J]. 无机盐工业, 2020, 52(11): 79-85.
ZHOU J W, CHENG B J, YU B Y, et al. Effect of heat-treated desulfurized gypsum on properties of super sulfated cement[J]. Inorganic Chemicals Industry, 2020, 52(11): 79-85 (in Chinese).
[20] GUO X L, SHI H S. Influence of thermally treated flue gas desulfurization (FGD) gypsum on performance of the slag powder concrete[J]. Journal of Wuhan University of Technology-Materials Science Edition, 2013, 28(6): 1122-1127.
[21] QI G Z, ZHANG Q, SUN Z N. Effect of calcium aluminate and carbide slag on mechanical property and hydration mechanism of supersulfated cement[J]. Buildings, 2024, 14(4): 930.
[22] SUN Z N, NIE S, ZHOU J, et al. Hydration mechanism of calcium sulfoaluminate-activated supersulfated cement[J]. Journal of Cleaner Production, 2022, 333: 130094.