全工业固废基高贝利特硫铝酸盐水泥熟料的制备与矿物形成微观机理

doi:10.16552/j.cnki.issn1001-1625.2025.0102

摘要/Abstract

摘要： 本文利用磷石膏、赤泥、铝灰、电石渣和煤矸石为原料制备全固废高贝利特硫铝酸盐水泥(HBSAC)。通过热重分析、XRD、SEM、抗压强度测试研究了制备HBSAC熟料的煅烧工艺,分析了熟料矿物反应过程和形成机理,并探究了HBSAC的力学性能。结果表明,HBSAC的最佳煅烧制度是以10 ℃/min升温至1 300 ℃,保温煅烧45 min。在该煅烧工艺下,HBSAC强度性能优越,1、3、7、28 d抗压强度分别可以达到29.1、40.1、42.1和54.0 MPa。通过控制矿物相发育状况调节HBSAC强度性能,当煅烧温度低于1 225 ℃时,大量无水硬性的过渡矿物残留,且硫铝酸四钙(C₄A₃)、硅酸二钙(C₂S)发育不完整,降低了HBSAC抗压强度;当煅烧温度为1 225~1 350 ℃时,铁相(C₄AF)的形成显著增加了液相含量,促进了离子扩散迁移,加速了目标矿物C₄A₃和C₂S形成。

关键词: 工业固废, 高贝利特硫铝酸盐水泥, 熟料矿物, 煅烧制度, 力学性能, 微观形貌

Abstract: This study utilized phosphogypsum, red mud, aluminum ash, carbide slag, and coal gangue as raw materials to prepare high belite sulphoaluminate cement (HBSAC) from solid waste. Through thermogravimetric analysis, XRD, SEM and compressive strength test, the calcination process of HBSAC clinker was studied, the reaction process and formation mechanism of clinker minerals were analyzed, and the mechanical properties of HBSAC were explored. The results demonstrate that the optimal calcination system involves heating at 10 ℃/min to 1 300 ℃ and keep the temperature for 45 min. Under this calcination process, the strength performance of HBSAC is excellent, and the compressive strength at 1, 3, 7 and 28 d can reach 29.1, 40.1, 42.1 and 54.0 MPa, respectively. The strength properties of HBSAC can be reguated by controlling the development of mineral phases. When the calcination temperature is below 1 225 ℃, residual non-hydraulic hardening transitional minerals exist. Incomplete crystallization of tetracalcium trialuminate sulfate (C₄A₃$\bar{S} $) and dicalcium silicate (C₂S) degrade the compressive strength of HBSAC. When the calcination temperature is 1 225~1 350 ℃, ferrite phase (C₄AF) formation enhances liquid phase content, facilitates ion diffusion and promotes the formation of target minerals C₄A₃$\bar{S} $ and C₂S.

Key words: industrial solid waste, high belite sulphoaluminate cement, clinker mineral, calcination system, mechanical property, microstructure

中图分类号:

TQ172

颜婉滢, 王东星, 聂利文. 全工业固废基高贝利特硫铝酸盐水泥熟料的制备与矿物形成微观机理[J]. 硅酸盐通报, 2025, 44(8): 2955-2964.

YAN Wanying, WANG Dongxing, NIE Liwen. Preparation of High Belite Sulphoaluminate Cement Clinker from Industrial Solid Waste and Microscopic Mechanism of Mineral Formation[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2025, 44(8): 2955-2964.

参考文献

[1] 中华人民共和国生态环境部. 生态环境状况公报: 2023中国生态环境状况公报[EB/OL]. (2024-06-05) [2025-03-26]. https://www.mee.gov.cn/hjzl/sthjzk/zghjzkgb/202406/P020240604551536165161.pdf.
Ministry of Ecology and Environment of the People's Republic of China. Report on the state of the environment in China: China's environmental status report 2023[EB/OL]. (2024-06-05) [2025-03-26]. https://www.mee.gov.cn/hjzl/sthjzk/zghjzkgb/202406/P020240604551536165161.pdf (in Chinese).
[2] LIU Y Q, GUO D W, DONG L, et al. Pollution status and environmental sound management (ESM) trends on typical general industrial solid waste[J]. Procedia Environmental Sciences, 2016, 31: 615-620.
[3] TANG J X, WANG Q W, CHOI G. Efficiency assessment of industrial solid waste generation and treatment processes with carry-over in China[J]. Science of the Total Environment, 2020, 726: 138274.
[4] TONG R, SUI T B, FENG L Z, et al. The digitization work of cement plant in China[J]. Cement and Concrete Research, 2023, 173: 107266.
[5] KAPLAN G, BAYRAKTAR O Y, LI Z G, et al. Improving the eco-efficiency of fiber reinforced composite by ultra-low cement content/high FA-GBFS addition for structural applications: minimization of cost, CO₂ emissions and embodied energy[J]. Journal of Building Engineering, 2023, 76: 107280.
[6] 中华人民共和国国家发展和改革委员会. 水泥行业节能降碳专项行动计划[EB/OL]. (2024-06-07) [2025-03-26]. https://www.ndrc.gov.cn/xxgk/zcfb/tz/202406/P020240607579153428151.pdf.
National Development and Reform Commission. Special action plan for energy saving and carbon reduction in the cement industry[EB/OL]. (2024-06-07) [2025-03-26]. https://www.ndrc.gov.cn/xxgk/zcfb/tz/202406/P020240607579153428151.pdf (in Chinese).
[7] KLEIB J, AOUAD G, BENZERZOUR M, et al. Effect of calcium sulfoaluminate cements composition on their durability[J]. Construction and Building Materials, 2021, 307: 124952.
[8] LV L Y, LUO S T, BRANKO Š, et al. Effect of particle size distribution on the pre-hydration, hydration kinetics, and mechanical properties of calcium sulfoaluminate cement[J]. Construction and Building Materials, 2023, 398: 132497.
[9] MORIN V, TERMKHAJORNKIT P, HUET B, et al. Impact of quantity of anhydrite, water to binder ratio, fineness on kinetics and phase assemblage of belite-ye'elimite-ferrite cement[J]. Cement and Concrete Research, 2017, 99: 8-17.
[10] XIN X Y, DUAN G B, ZHU J, et al. Study on the properties of belite calcium sulfoaluminate cement-ordinary Portland cement composite cementitious system[J]. Buildings, 2024, 14(4): 890.
[11] GU X Y, TAN H B, HE X Y, et al. Utilization of carbide slag by wet grinding as an accelerator in calcium sulfoaluminate cement[J]. Materials, 2020, 13(20): 4526.
[12] WANG Y L, DONG S J, LIU L L, et al. Study formation process of cement clinker minerals by using calcium carbide slag as raw material[J]. Applied Mechanics and Materials, 2013, 389: 341-345.
[13] 裘国华, 施正伦, 余春江, 等. 煤矸石代黏土煅烧水泥熟料配方优化试验研究[J]. 浙江大学学报(工学版), 2010, 44(1): 130.
QIU G H, SHI Z L, YU C J, et al. Experimental research on utilization of coal gangue as clay for optimized formula on cement clinker calcination[J]. Journal of Zhejiang University (Engineering Science), 2010, 44(1): 130 (in Chinese).
[14] 郭伟, 王春, 孙佳胜, 等. 硫铝酸钙-贝利特水泥熟料的低温制备及其水化性能研究[J]. 材料导报, 2017, 31(24): 35-39.
GUO W, WANG C, SUN J S, et al. Study on low-temperature preparation and hydration properties of calcium sulphoaluminate-belite cement clinker[J]. Materials Review, 2017, 31(24): 35-39 (in Chinese).
[15] 兰明章, 陈智丰, 张振秋, 等. 一种利用煤矸石制备的高贝利特硫铝酸盐水泥: CN101786812A[P]. 2010-07-28.
LAN M Z, CHEN Z F, ZHANG Z Q, et al. A kind of high belite sulphoaluminate cement prepared from coal gangue: CN101786812A[P]. 2010-07-28 (in Chinese).
[16] 梁娇, 楚婉怡, 黄永波, 等. 预分解磷石膏制备贝利特-硫铝酸盐水泥[J]. 材料导报, 2017, 31(24): 1-5.
LIANG J, CHU W Y, HUANG Y B, et al. Preparation of belite-sulphoaluminate cement from pre-decomposed phosphogypsum[J]. Material Bulletin, 2017, 31(24): 1-5 (in Chinese).
[17] ZHANG P, ZHANG B X, CHANG J, et al. Investigation of process parameters of phosphogypsum for preparing calcium sulfoaluminate cement[J]. Buildings, 2022, 12(11): 1774.
[18] WANG W L, WANG X J, ZHU J P, et al. Experimental investigation and modeling of sulfoaluminate cement preparation using desulfurization gypsum and red mud[J]. Industrial & Engineering Chemistry Research, 2013, 52(3): 1261-1266.
[19] 夏瑞杰, 朱建平, 刘少雄, 等. 赤泥和脱硫石膏制备高贝利特硫铝酸盐水泥熟料[J]. 有色金属工程, 2017, 7(6): 58-63+79.
XIA R J, ZHU J P, LIU S X, et al. Preparation of high belite sulphoaluminate cement clinkers using red mud and desulfurization gypsum[J]. Nonferrous Metals Engineering, 2017, 7(6): 58-63+79 (in Chinese).
[20] WANG Z, LI J Z, HUANG S W, et al. Effect of Al₂O₃/SiO₂ ratio on the chroma and phase compositions of white sulfoaluminate cement clinker[J]. Construction and Building Materials, 2022, 345: 128202.
[21] 刘辉敏. 水泥生产技术基础[M]. 2版. 北京: 化学工业出版社, 2016.
LIU H M. Basic of cement production technology[M]. 2nd ed. Beijing: Chemical Industry Press, 2016 (in Chinese).
[22] HUANG Y B, QIAN J S, LIANG J, et al. Characterization and calorimetric study of early-age hydration behaviors of synthetic ye'elimite doped with the impurities in phosphogypsum[J]. Journal of Thermal Analysis and Calorimetry, 2016, 123(2): 1545-1553.
[23] WU S, YAO Y G, YAO X L, et al. Co-preparation of calcium sulfoaluminate cement and sulfuric acid through mass utilization of industrial by-product gypsum[J]. Journal of Cleaner Production, 2020, 265: 121801.
[24] CUESTA A, DE LA TORRE A G, LOSILLA E R, et al. Structure, atomistic simulations, and phase transition of stoichiometric yeelimite[J]. Chemistry of Materials, 2013, 25(9): 1680-1687.
[25] 宋飞, 俞为民, 姚丕强, 等. C₂S-C₄A₃水泥熟料的矿物组成[J]. 南京工业大学学报(自然科学版), 2014, 36(4): 29-33.
SONG F, YU W M, YAO P Q, et al. Mineral composition of C₂S-C₄A₃ clinker[J]. Journal of Nanjing Tech University (Natural Science Edition), 2014, 36(4): 29-33 (in Chinese).
[26] LI J Y, CHANG J. Effect of crystal/amorphous ratio on mechanical properties in a-C₂S hydration system with or without gypsum addition[J]. Construction and Building Materials, 2019, 208: 36-45.
[27] ZHANG H, LI J J, KANG F. Real-time monitoring of humidity inside concrete structures utilizing embedded smart aggregates[J]. Construction and Building Materials, 2022, 331: 127317.
[28] 王明明. 煤矸石制备高贝利特硫铝酸盐水泥试验研究[D]. 西安: 西安建筑科技大学, 2023.
WANG M M. Experimental study on preparation of high belite sulphoaluminate cement from coal gangue[D]. Xi'an: Xi'an University of Architecture and Technology, 2023 (in Chinese).
[29] 谭俊华, 史熙亮, 朱开金, 等. 利用低品位铝矾土和铸造废砂制备高贝利特硫铝酸盐水泥的研究[J]. 硅酸盐通报, 2017, 36(12): 4284-4290+4301.
TAN J H, SHI X L, ZHU K J, et al. Preparation of high belite sulphoaluminate cement by low grade bauxite and foundry waste sand[J]. Bulletin of the Chinese Ceramic Society, 2017, 36(12): 4284-4290+4301 (in Chinese).
[30] WANG X L, GUO M Z, YUE G B, et al. Synthesis of high belite sulfoaluminate cement with high volume of mixed solid wastes[J]. Cement and Concrete Research, 2022, 158: 106845.
[31] 瞿海洋. 铁相对贝利特硫铝酸盐水泥制备与性能影响研究[D]. 北京: 北京工业大学, 2018.
QU H Y. Study on the influence of iron phase on the preparation and properties of belite sulphoaluminate cement[D]. Beijing: Beijing University of Technology, 2018 (in Chinese).
[32] LUDWIG H M, ZHANG W S. Research review of cement clinker chemistry[J]. Cement and Concrete Research, 2015, 78: 24-37.
[33] ISTERI V, OHENOJA K, HANEIN T, et al. Ferritic calcium sulfoaluminate belite cement from metallurgical industry residues and phosphogypsum: clinker production, scale-up, and microstructural characterisation[J]. Cement and Concrete Research, 2022, 154: 106715.