磷石膏与冶金污酸石膏渣处理处置研究进展

Research progress on comprehensive utilization of phosphogypsum and metallurgical acidic gypsum residue

  • 摘要: 磷石膏与冶金污酸石膏渣分别是磷肥生产和污酸中和产生的以CaSO4·2H2O为主要成分的固体废物. 加快对二者的综合利用对于资源回收和环境保护至关重要. 目前,磷石膏在建筑、化工和农业领域具有广泛的应用,但大规模消纳仍面临挑战. 而污酸石膏渣因含有砷、镉、铅等毒害元素而处理困难,消纳的重点为固化/稳定化处置. 本文首次构建了磷石膏与污酸石膏渣的对比框架,综述了两类石膏渣的综合利用现状,深入探讨了不同产品体系中的资源化利用机理及其所含重金属等污染物的固定机制,并对未来发展提出了建议与展望. 未来应着力研发高效低成本稳定磷石膏中可溶性磷、氟的技术,扩大磷石膏的高值化利用规模,开发制备石膏晶须、合成新型化学原料等新领域;污酸石膏渣应重点开发有价金属元素回收技术,实现产业化应用. 加强探索污酸石膏渣与其他固废的协同利用技术,响应国家“以废治废”的发展方向. 对石膏渣固化体展开长效性研究,防止“反溶”等问题的发生. 同时,优化高效络合剂与沉淀剂的应用,通过酸性污水处理过程调控,从源头减少石膏渣产量及其污染物含量.

     

    Abstract: The production of various industrial by-products in the form of gypsum residues increases annually with the acceleration of industrialization. China, as a large agricultural and non-ferrous metal smelting country, produces a large amount of solid waste with CaSO4·2H2O as the main component in both phosphate fertilizer production and dirty acid neutralization. These gypsum residues occupy a large amount of land resources and are responsible for heavy-metal leakage, the release of toxic gases, and other safety hazards. Thus, accelerating the comprehensive utilization of these two types of gypsum residues is not only directly in line with the strategic layout for the construction of a “Waste-Free City” and the “Double Carbon” goal, but would also significantly contribute to resource recycling and ecological environmental protection. At present, phosphogypsum has a wide range of applications in the fields of construction, the chemical industry, and agriculture, and is widely used in the preparation of cement retarders, quicklime, road base materials, soil conditioners, and so on. However, its comprehensive utilization rate is only approximately 40%, and there are still large phosphogypsum stockpiles. It is crucial to expand the market demand for phosphogypsum applications, and the key lies in the efficient removal of its impurities. On the other hand, the gypsum residue produced by acidic wastewater neutralization is difficult to handle because of the presence of toxic elements such as arsenic, cadmium, and lead. Thus, at present, its disposal primarily consists of the recovery of valuable metals and solidification/stabilization. However, because of the complex composition and low content of these valuable metals, the economic benefits of recovery are insufficient and it is difficult to realize industrialization. This paper presents a framework for comparing phosphogypsum and acidic wastewater neutralization gypsum residues for the first time, systematically discusses their current utilization and disposal methods, and thoroughly explores the resource-utilization mechanisms of different production systems, along with the fixation mechanisms for heavy metals and other pollutants. Finally, some suggestions and future prospects are outlined based on this review. Efforts should be made to research and develop highly efficient and low-cost technologies to stabilize the soluble phosphorus and fluorine in phosphogypsum to ensure that its leachate meets the requirements for surface water class V and above, while simultaneously exploring the development of emerging fields such as gypsum whisker preparation and the synthesis of new chemical raw materials, with the goal of expanding the scale of the high-value utilization of phosphogypsum and realizing large-scale phosphogypsum elimination. The following future development steps for tainted acid gypsum residues are proposed: 1) continue to develop green and efficient valuable metal element recovery technology, and achieve large-scale industrial application; 2) strengthen the exploration of synergistic use technology between tainted acid gypsum residues and other solid wastes, and synergistically treat gypsum slag with other solid wastes in combination with other methods such as flotation to improve resource utilization; 3) optimize the application of efficient complexing and precipitating agents to reduce gypsum production and its pollutant content at the source through acidic wastewater treatment process regulation; and 4) increase the attention given to studies of the longevity of a gypsum slag curing body to prevent the occurrence of an “anti-solution” and other problems.

     

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