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磷石膏與冶金污酸石膏渣處理處置研究進展

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

  • 摘要: 磷石膏與冶金污酸石膏渣分別是磷肥生產和污酸中和產生的以CaSO4·2H2O為主要成分的固體廢物. 加快對二者的綜合利用對于資源回收和環境保護至關重要. 目前,磷石膏在建筑、化工和農業領域具有廣泛的應用,但大規模消納仍面臨挑戰. 而污酸石膏渣因含有砷、鎘、鉛等毒害元素而處理困難,消納的重點為固化/穩定化處置. 本文首次構建了磷石膏與污酸石膏渣的對比框架,綜述了兩類石膏渣的綜合利用現狀,深入探討了不同產品體系中的資源化利用機理及其所含重金屬等污染物的固定機制,并對未來發展提出了建議與展望. 未來應著力研發高效低成本穩定磷石膏中可溶性磷、氟的技術,擴大磷石膏的高值化利用規模,開發制備石膏晶須、合成新型化學原料等新領域;污酸石膏渣應重點開發有價金屬元素回收技術,實現產業化應用. 加強探索污酸石膏渣與其他固廢的協同利用技術,響應國家“以廢治廢”的發展方向. 對石膏渣固化體展開長效性研究,防止“反溶”等問題的發生. 同時,優化高效絡合劑與沉淀劑的應用,通過酸性污水處理過程調控,從源頭減少石膏渣產量及其污染物含量.

     

    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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