磷石膏固化剂的种类及其作用机理研究进展
Progress of Research on Types of Phosphogypsum Curing Agents and Their Mechanism of Action
DOI: 10.12677/ms.2025.159193, PDF,   
作者: 徐海根*, 潘羽翔, 高煜臻, 段 平#：中国地质大学(武汉)，材料与化学学院，湖北 武汉；徐 志, 李作斌：湖北九厦低碳产业发展研究院有限公司，湖北 宜昌
关键词: 磷石膏；固化剂；力学性能；作用机理；Phosphogypsum； Curing Agent； Mechanical Properties； Mechanism of Action
摘要: 磷石膏是湿法生产磷酸过程中产生的一种工业废弃物，其大量堆存不仅占用土地资源，还会对环境造成污染。为提高磷石膏的资源化利用率，本文综述了无机和有机固化剂在磷石膏固化中的应用及其作用机理。无机固化剂包括水泥、石灰和复合材料固化剂，主要通过生成钙矾石(AFt)、水合硅酸钙(C-S-H)和水合铝酸钙(C-A-H)等水化产物，填充孔隙并增强磷石膏的力学性能和耐水性。有机固化剂如不饱和聚酯树脂(UPR)、环氧树脂和聚丙烯酸钠等，通过形成高分子三维交联网状结构或静电排斥作用，改善磷石膏的微观结构和稳定性。本文详细分析了不同固化剂的配比和种类对磷石膏抗压强度、抗拉强度及微观结构的影响，并总结了各种固化剂的作用机理，为磷石膏的资源化利用提供了理论依据和技术支持。
Abstract: Phosphogypsum is a kind of industrial waste produced in the process of wet production of phosphoric acid, and its large amount of stockpiling not only occupies land resources, but also causes pollution to the environment. In order to improve the resource utilisation of phosphogypsum, this paper reviews the application of inorganic and organic curing agents in phosphogypsum curing and their mechanism of action. Inorganic curing agents, including cement, lime and composite curing agents, fill pores and enhance the mechanical properties and water resistance of phosphogypsum, mainly through the generation of hydration products such as calcium alumina (AFt), hydrated calcium silicate (C-S-H) and hydrated calcium aluminate (C-A-H). Organic curing agents such as unsaturated polyester resins (UPR), epoxy resins and sodium polyacrylate improve the microstructure and stability of phosphogypsum through the formation of a polymer three-dimensional cross-linked mesh structure or electrostatic repulsion. This paper analyses in detail the effects of different curing agent ratios and types on the compressive strength, tensile strength and microstructure of phosphogypsum, and summarizes the action mechanism of various curing agents, which provides a theoretical basis and technical support for the resourceful use of phosphogypsum.
文章引用：徐海根, 潘羽翔, 高煜臻, 徐志, 李作斌, 段平. 磷石膏固化剂的种类及其作用机理研究进展[J]. 材料科学, 2025, 15(9): 1814-1824. https://doi.org/10.12677/ms.2025.159193

参考文献

[1] 王莹, 方俊文, 高鹏. 2023年我国磷复肥行业运行情况及发展趋势[J]. 生态产业科学与磷氟工程, 2024, 39(7): 1-8.
[2] 崔荣政, 王臣, 修学峰. 2023年我国磷石膏综合利用情况及产业发展现状分析[J]. 生态产业科学与磷氟工程, 2024, 39(11): 1-6.
[3] Jha, A.K. and Sivapullaiah, P.V. (2016) Volume Change Behavior of Lime Treated Gypseous Soil—Influence of Mineralogy and Microstructure. Applied Clay Science, 119, 202-212. [Google Scholar] [CrossRef] 
[4] Chen, Y., Wang, L., Song, P. and Wang, Q. (2017) Effects of Magnesium Potassium Phosphate Cements Mixed with Silica Fume on the Solidification and Reduction of Municipal Sludge. IOP Conference Series: Materials Science and Engineering, 167, Article 012003. [Google Scholar] [CrossRef] 
[5] Ji, X., Dai, C., Cui, Z., et al. (2021) Research on Engineering Characteristics of Curing Agent Stabilized Phosphogypsum Roadbed Filler. China Journal of Highway and Transport, 34, 225-233.
[6] Fu, R., Lu, Y., Wang, L., An, H., Chen, S. and Kong, D. (2024) The Effects of Admixtures on the Durability Properties of Phosphogypsum-Based Cementitious Materials. Construction and Building Materials, 411, Article 134379. [Google Scholar] [CrossRef] 
[7] 黄绪泉, 蔡家伟, 赵小蓉, 等. 硅酸钠改性磷石膏道路稳定材料性能及固化机理[J]. 硅酸盐通报, 2024, 43(12): 4471-4479.
[8] Chen, P., Ma, B., Tan, H., Lv, Z., Li, M. and Wu, L. (2023) Utilization of Tricalcium Aluminate as Modifier on Phosphogypsum-Based Full Solid-Waste Cementitious Material. Construction and Building Materials, 377, Article 131034. [Google Scholar] [CrossRef] 
[9] Ye, S., Feng, P., Liu, Y., Liu, J. and Bullard, J.W. (2020) Dissolution and Early Hydration of Tricalcium Aluminate in Aqueous Sulfate Solutions. Cement and Concrete Research, 137, Article 106191. [Google Scholar] [CrossRef] 
[10] Zhang, P., Ouyang, S., Li, P., Sun, Z., Ding, N. and Huang, Y. (2020) Ultrahigh Removal Performance of Lead from Wastewater by Tricalcium Aluminate via Precipitation Combining Flocculation with Amorphous Aluminum. Journal of Cleaner Production, 246, Article 118728. [Google Scholar] [CrossRef] 
[11] Collins, P.J., Grugel, R.N. and Radlińska, A. (2021) Hydration of Tricalcium Aluminate and Gypsum Pastes on the International Space Station. Construction and Building Materials, 285, Article 122919. [Google Scholar] [CrossRef] 
[12] Wang, Y., Xu, L., He, X., Su, Y., Miao, W., Strnadel, B., et al. (2022) Hydration and Rheology of Activated Ultra-Fine Ground Granulated Blast Furnace Slag with Carbide Slag and Anhydrous Phosphogypsum. Cement and Concrete Composites, 133, Article 104727. [Google Scholar] [CrossRef] 
[13] Chen, P., Ma, B., Tan, H., Wu, L., Zheng, Z., He, X., et al. (2022) Improving the Mechanical Property and Water Resistance of β-Hemihydrate Phosphogypsum by Incorporating Ground Blast-Furnace Slag and Steel Slag. Construction and Building Materials, 344, Article 128265. [Google Scholar] [CrossRef] 
[14] Huang, Y. and Lin, Z. (2010) Investigation on Phosphogypsum-Steel Slag-Granulated Blast-Furnace Slag-Limestone Cement. Construction and Building Materials, 24, 1296-1301. [Google Scholar] [CrossRef] 
[15] Hu, Y., Ren, X., Ye, J., Luan, Z. and Zhang, W. (2022) The Reactive Products and Reactivity of Modified Red Mud and Ground Granulated Blast Furnace Slag at Different Alkalinities. Construction and Building Materials, 346, Article 128471. [Google Scholar] [CrossRef] 
[16] Zhou, Y., Pu, S., Han, F., Zhang, H. and Zhang, Z. (2022) Effect of Ultrafine Slag on Hydration Heat and Rheology Properties of Portland Cement Paste. Powder Technology, 405, Article 117549. [Google Scholar] [CrossRef] 
[17] Qin, X., Cao, Y., Guan, H., Hu, Q., Liu, Z., Xu, J., et al. (2023) Resource Utilization and Development of Phosphogypsum-Based Materials in Civil Engineering. Journal of Cleaner Production, 387, Article 135858. [Google Scholar] [CrossRef] 
[18] Lin, R., Huang, G., Ma, F., Pan, T., Wang, X., Han, Y., et al. (2024) Investigation of Phosphogypsum-Based Cementitious Materials: The Effect of Lime Modification. Developments in the Built Environment, 18, Article 100477. [Google Scholar] [CrossRef] 
[19] Chen, Y., Ji, X., Cui, Z., Ye, Y., He, S., Zhou, H., et al. (2024) Investigation on Engineering Characteristics of Lime-Stabilized Phosphogypsum Subgrade Filler. Journal of Materials in Civil Engineering, 36, Article 04024028. [Google Scholar] [CrossRef] 
[20] Zhang, M., Mei, Y., Li, Y. and Xia, J. (2024) Research on the Technology and Mechanism of Direct Acidification of Phosphogypsum and Deeply Solidify Impurities with Lime. Journal of Environmental Chemical Engineering, 12, Article 114937. [Google Scholar] [CrossRef] 
[21] Li, B., Shu, J.H., Chen, M.J., et al, (2023) A New Basic Burning Raw Material for Simultaneous Stabilization/Solidification of PO43-P and F in Phosphogypsum. Ecotoxicology and Environmental Safety, 252, Article 114582. [Google Scholar] [CrossRef] [PubMed]
[22] 李丹丹, 程寅, 李德高, 等. 大掺量磷石膏路基填料的性能研究与工程应用[J]. 新型建筑材料, 2024, 51(11): 55-61.
[23] Huang, S.Y., Liu, W.H., Li, W.G., et al. (2024) Study on Water Resistance of Phosphogypsum Solidified by Magnesium Oxychloride Cement (MOC) and NaHCO3. Construction and Building Materials, 451, Article 138877. [Google Scholar] [CrossRef] 
[24] Shen, W.G., Zhou, M.K., Ma, W., et al. (2009) Investigation on the Application of Steel Slag-Fly Ash-Phosphogypsum Solidified Material as Road Base Material. Journal of Hazardous Materials, 164, 99-104. [Google Scholar] [CrossRef] [PubMed]
[25] Ma, F.Y., Chen, L.L., Lin, Z.W., et al. (2022) Microstructure and Key Properties of Phosphogypsum-Red Mud-Slag Composite Cementitious Materials. Materials, 15, Article 6096. [Google Scholar] [CrossRef] [PubMed]
[26] Wu, F.H., Jin, C.Y., Qu, G.F., et al. (2022) Enhancement of Phosphogypsum Mechanical Block with the Addition of Iron and Aluminum Salts. Journal of Building Engineering, 52, Article 104397. [Google Scholar] [CrossRef] 
[27] Chen, Q.S., Zhang, Q., Wangy, M., et al. (2022) Highly-Efficient Fluoride Retention in On-Site Solidification/Stabilization of Phosphogypsum: Cemented Paste Backfill Synergizes with Poly-Aluminum Chloride Activation. Chemosphere, 309, Article 136652.
[28] 郭逢治, 薛中群. 关于防止室温固化不饱和聚酯树脂表面发粘的探讨[J]. 热固性树脂, 1995(2): 42-46.
[29] Tabatabai, H., Janbaz, M. and Nabizadeh, A. (2018) Mechanical and Thermo-Gravimetric Properties of Unsaturated Polyester Resin Blended with FGD Gypsum. Construction and Building Materials, 163, 438-445. [Google Scholar] [CrossRef] 
[30] 邹萌, 何兆益, 唐亮, 等. 不饱和聚酯树脂固化磷石膏强度形成机制及微观特性研究[J]. 应用化工, 2024, 53(9): 2109-2113+2117.
[31] Nguyen, S.A., Dong, T.Q., Doan, M.Q., et al. (2023) Boosting the Ultraviolet Shielding and Thermal Retardancy Properties of Unsaturated Polyester Resin by Employing Electrochemically Exfoliated E-Go Nanosheets. RSC Advances, 13, 25762-25777. [Google Scholar] [CrossRef] [PubMed]
[32] 陶果, 曾琪, 陈自然, 等. 环氧树脂固化剂研究现状与发展趋势[J]. 广东化工, 2012, 39(16): 100-101.
[33] An, H.F., Wang, L.L., Lv, F.T., et al. (2023) Multi-Objective Optimization of Properties on Polymer Fiber-Reinforced Desulfurization Gypsum-Based Composite Cementitious Materials. Construction and Building Materials, 369, Article 130590. [Google Scholar] [CrossRef] 
[34] Kowalska, E., Wielgosz, Z., Zubrowska, M., Pasynkiewicz, S. and Choros, M. (2004) Application of Waste Phosphogypsum in Thermoplastic and Chemosetting Composites. Polimery, 49, 828-836. [Google Scholar] [CrossRef] 
[35] 何晓琴, 杨帆, 陈聪地, 等. 环氧树脂固化剂在免烧磷石膏砖中的应用探索[J]. 广州化工, 2022, 50(5): 44-47.
[36] Manzur, T., Iffat, S. and Noor, M.A. (2015) Efficiency of Sodium Polyacrylate to Improve Durability of Concrete under Adverse Curing Condition. Advances in Materials Science and Engineering, 2015, 1-8. [Google Scholar] [CrossRef] 
[37] Min, C.D., Liu, Z.X., Shi, Y., et al. (2023) Improving the Strength Performance of Cemented Phosphogypsum Backfill with Sulfate-Resistant Binders. Construction and Building Materials, 409, Article 133974. [Google Scholar] [CrossRef] 
[38] Mardani-Aghabaglou, A., Boyacı, O.C., Hosseinnezhad, H., Felekoğlu, B. and Ramyar, K. (2016) Effect of Gypsum Type on Properties of Cementitious Materials Containing High Range Water Reducing Admixture. Cement and Concrete Composites, 68, 15-26. [Google Scholar] [CrossRef] 
[39] Zhou, Z.B., Liu, J.O., Luo, K., et al. (2021) Study on Performance Regulation and Mechanism of Quicklime and Biopolymer on Hemihydrate Phosphogypsum. Journal of Renewable Materials, 10, 373-384. [Google Scholar] [CrossRef] 
[40] 赵明星, 吴建辉, 龙宝林, 等. 有机无机复合固化剂稳定磷石膏路基填料的性能研究[J]. 新型建筑材料, 2024, 51(12): 101-107.
[41] Zhou, W., Ye, Q., Shi, S.Q., Fang, Z., Gao, Q. and Li, J. (2021) A Strong Magnesium Oxychloride Cement Wood Adhesive via Organic-Inorganic Hybrid. Construction and Building Materials, 297, Article 123776. [Google Scholar] [CrossRef] 
[42] Ren, H., Liu, W. and Zhang, D. (2021) Application of Phosphogypsum to Solidification of Silty Soil: Mechanical Properties and Microstructure. Mechanics of Advanced Materials and Structures, 29, 6026-6038. [Google Scholar] [CrossRef] 

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