磷尾矿基地质聚合物的制备与界面状态研究

Preparation and interface state of phosphate tailing-based geopolymers

摘要

磷尾矿的长期堆存会占用大量土地, 污染土壤及地下水, 它的无害化处置十分必要. 本研究以磷尾矿为主要原料, 粉煤灰为活性硅铝材料, 水玻璃为碱性激发剂, 在磷尾矿和粉煤灰固体掺量分别为60%和40%, 水灰比为0.22的条件下, 制备得到抗压强度为38.8 MPa的高性能地质聚合物. XRD、 FTIR、 SEM-EDS、 XPS等分析结果表明, 磷尾矿与碱性激发剂的反应活性较弱, 硅铝材料则能够与碱性激发剂反应生成沸石和凝胶, 并包裹/覆盖磷尾矿形成结构致密的磷尾矿基地质聚合物. 在地质聚合物的形成过程中, 部分铝氧四面体取代了硅氧四面体, 引起地质聚合物之间的缩聚反应, 增加了地质聚合物的强度. 浸出毒性试验结果表明地质聚合物对重金属离子具有良好的固封效果. 因此, 磷尾矿基地质聚合物具有抗压强度高、 固封性能好的优点, 以磷尾矿制备地质聚合物是缓解堆存压力、 实现磷尾矿资源化利用的重要途径.

Abstract

The long-term storage of phosphate tailings will occupy a large amount of land, pollute soil and groundwater, thus, it is crucial to achieve the harmless disposal of phosphate tailings. In this study, high-performance geopolymers with compressive strength of 38.8 MPa were prepared by using phosphate tailings as the main raw material, fly ash as the active silicon-aluminum material, and water glass as the alkaline activator. The solid content of phosphate tailings and fly ash was 60% and 40%, respectively, and the water-cement ratio was 0.22. The results of XRD, FTIR, SEM-EDS and XPS show that the reactivity of phosphate tailings with alkaline activator is weak, and the silicon-aluminum material can react with alkaline activator to form zeolite and gel, and encapsulate/cover the phosphate tailings to form a dense phosphate tailings-based geopolymer. During the formation of geopolymers, part of the aluminum-oxygen tetrahedron replaced the silicon-oxygen tetrahedron, causing the polycondensation reaction between geopolymers and increasing the strength of geopolymers. The leaching toxicity test results show that the geopolymer has a good solid sealing effect on heavy metal ions. The preparation of geopolymer from phosphate tailings is an important way to alleviate the storage pressure and realize the resource utilization of phosphate tailings.

Keywords

phosphate tailing / geopolymer / interface state / toxicity leaching

参考文献

[[1]] Yu H-x, Zahidi I, Fai C M. Reclaiming abandoned mine tailings ponds for agricultural use: Opportunities and challenges. Environmental Research, 2023, 232: 116336, J]

[[2]] Zhang N, Tang B-w, Liu X-ming. Cementitious activity of iron ore tailing and its utilization in cementitious materials, bricks and concrete. Construction and Building Materials, 2021, 288: 123022, J]

[[3]] Guo D-f, Hou H-m, Long J, et al.. Underestimated environmental benefits of tailings resource utilization: Evidence from a life cycle perspective. Environmental Impact Assessment Review, 2022, 96: 106832, J]

[[4]] Saira G C, Shanthakumar S. Zero waste discharge in tannery industries - An achievable reality? A recent review. Journal of Environmental Management, 2023, 335: 117508, J]

[[5]] Hu N-y, Lv Y-f, Luo B-y, et al.. Preparation and performance of porous ceramsite for Ag⁺ removal in sewage treatment with total phosphorus tailings. Journal of Cleaner Production, 2023, 413: 137515, J]

[[6]] Yu Y-h, Du C-m, Yang Xiao. Recovery of phosphorus from steelmaking slag and phosphate tailings by a collaborative processing method. Separation and Purification Technology, 2023, 313: 123499, J]

[[7]] Chen Q-s, Zhang Q-l, Fourie A, et al.. Utilization of phosphogypsum and phosphate tailings for cemented paste backfill. Journal of Environmental Management, 2017, 201: 19-27, J]

[[8]] Chen W, Yin S-h, Chen X, et al.. Study on comprehensive utilization of tailings by using bioleaching and microbial-cementation. Case Studies in Construction Materials, 2023, 18: e02190, J]

[[9]] Lin S-j, Zheng Y-j, Liu W-b, et al.. Consolidation of phosphorus tailings and soluble fluorine & phosphorus with calcium carbide residue-mirabilite waste as a green alkali activator. Case Studies in Construction Materials, 2023, 18: e01779, J]

[[10]] Abdel-Aal E S A. Recovery of phosphoric acid from Egyptian Nile Valley phosphate tailings. Minerals Engineering, 2000, 13(2): 223-226, J]

[[11]] Huang Y, Hu N-y, Ye Y-c, et al.. Preparation and pore-forming mechanism of MgO-Al₂O₃-CaO-based porous ceramics using phosphorus tailings. Ceramics International, 2022, 48(20): 29882-29891, J]

[[12]] Zheng K-r, Zhou J, Gbozee M. Influences of phosphate tailings on hydration and properties of Portland cement. Construction and Building Materials, 2015, 98: 593-601, J]

[[13]] Zhou K-q, Zhou Q-q, Gong K-l, et al.. Waste-to-resource strategy to fabricate environmentally benign flame retardants from waste phosphorus tailings. Composites Communications, 2020, 19: 173-176, J]

[[14]] Yang Y-h, Wei Z-a, Chen Y-l, et al.. Utilizing phosphate mine tailings to produce ceramisite. Construction and Building Materials, 2017, 155: 1081-1090, J]

[[15]] Guo C-s, Chen W, Deng T-fei. Fundamental study on the preparation of insulating ceramics via the phase reconstruction of phosphate tailings. Ceramics International, 2023, 49(6): 9419-9431, J]

[[16]] Gu K, Chen B, Yan P, et al.. Recycling of phosphate tailings and acid wastewater from phosphorus chemical industrial chain to prepare a high value-added magnesium oxysulfate cement. Journal of Cleaner Production, 2022, 369: 133343, J]

[[17]] Jin C-y, Chen B-j, Qu G-f, et al.. NaHCO₃ synergistic electrokinetics extraction of F, P, and Mn from phosphate ore flotation tailings. Journal of Water Process Engineering, 2023, 54: 104013, J]

[[18]] Moukannaa S, Loutou M, Benzaazoua M, et al.. Recycling of phosphate mine tailings for the production of geopolymers. Journal of Cleaner Production, 2018, 185: 891-903, J]

[[19]] Xu H, Van Deventer J S J. The geopolymerisation of alumino-silicate minerals. International Journal of Mineral Processing, 2000, 59(3): 247-266, J]

[[20]] Zribi M, Baklouti S. Investigation of Phosphate based geopolymers formation mechanism. Journal of Non-Crystalline Solids, 2021, 562: 120777, J]

[[21]] Ahmad Zaidi F H, Ahmad R, Al Bakri Abdullah M M, et al.. Geopolymer as underwater concreting material: A review. Construction and Building Materials, 2021, 291: 123276, J]

[[22]] Cong P-l, Cheng Y-qian. Advances in geopolymer materials: A comprehensive review. Journal of Traffic and Transportation Engineering (English Edition), 2021, 8(3): 283-314, J]

[[23]] Singh N B, Middendorf B. Geopolymers as an alternative to Portland cement: An overview. Construction and Building Materials, 2020, 237: 117455, J]

[[24]] Topçu Ï B, Toprak M U, Uygunoğlu T. Durability and microstructure characteristics of alkali activated coal bottom ash geopolymer cement. Journal of Cleaner Production, 2014, 81: 211-217, J]

[[25]] Tahir M F M, Al Bakri Abdullah M M, Rahim S Z A, et al.. Mechanical and durability analysis of fly ash based geopolymer with various compositions for rigid pavement applications. Materials, 2022, 15(10): 3458, J]

[[26]] Krishna R S, Mishra J, Zribi M, et al.. A review on developments of environmentally friendly geopolymer technology. Materialia, 2021, 20: 101212, J]

[[27]] Krishna R S, Shaikh F, Mishra J, et al.. Mine tailings-based geopolymers: Properties, applications and industrial prospects. Ceramics International, 2021, 47(13): 17826-17843, J]

[[28]] He X, Yuhua Z-h, Qaidi S, et al.. Mine tailings-based geopolymers: A comprehensive review. Ceramics International, 2022, 48(17): 24192-24212, J]

[[29]] Zhao J-h, Tong L-y, Li B-e, et al.. Eco-friendly geopolymer materials: A review of performance improvement, potential application and sustainability assessment. Journal of Cleaner Production, 2021, 307: 127085, J]

[[30]] Xu J, Kang A-h, Wu Z-g, et al.. The effect of mechanical-thermal synergistic activation on the mechanical properties and microstructure of recycled powder geopolymer. Journal of Cleaner Production, 2021, 327: 129477, J]

[[31]] Burduhos Nergis D D, Vizureanu P, Sandu A V, et al.. XRD and TG-DTA study of new phosphate-based geopolymers with coal ash or metakaolin as aluminosilicate source and mine tailings addition. Materials, 2021, 15(1): 202, J]

[[32]] Idrees M, Ameen A, Shi J-y, et al.. Preparation and performance optimization of eco-friendly geopolymers prepared from coarser lignite-based waste fly ash. Construction and Building Materials, 2023, 391: 131804, J]

[[33]] Zhang J-r, Fu Y, Wang A, et al.. Research on the mechanical properties and microstructure of fly ash-based geopolymers modified by molybdenum tailings. Construction and Building Materials, 2023, 385: 131530, J]

[[34]] Ramli M I I, Salleh M A A M, Abdullah M M A B, et al.. The influence of sintering temperature on the pore structure of an alkali-activated Kaolin-based geopolymer ceramic. Materials, 2022, 15(7): 2667, J]

[[35]] Mao N-n, Wu D-z, Chen K-y, et al.. Combining experiments and molecular dynamics simulations to investigate the effects of water on the structure and mechanical properties of a coal gangue-based geopolymer. Construction and Building Materials, 2023, 389: 131556, J]

[[36]] Fan J-y, Yan J-h, Zhou M-y, et al.. Heavy metals immobilization of ternary geopolymer based on nickel slag, lithium slag and metakaolin. Journal of Hazardous Materials, 2023, 453: 131380, J]

[[37]] Gíngör D, Özen S. Development and characterization of clinoptilolite-, mordenite-, and analcime-based geopolymers: A comparative study. Case Studies in Construction Materials, 2021, 15: e00576, J]

[[38]] Wang Q, Kang S-r, Wu L-m, et al.. Molecular simulation of N-A-S-H and C-A-S-H in geopolymer cementitious system. Journal of Building Materials, 2020, 23(1): 184-191 [J]

[[39]] Saptamongkol A, Sata V, Wongsa A, et al.. Hybrid geopolymer paste from high calcium fly ash and glass wool: Mechanical, microstructure, and sulfuric acid and magnesium sulfate resistance characteristics. Journal of Building Engineering, 2023, 76: 107245, J]

[[40]] Addis L B, Sendekie Z B, Habtu N G, et al.. Optimization of process parameters for the synthesis of class F fly ash-based geopolymer binders. Journal of Cleaner Production, 2023, 415: 137849, J]

[[41]] Bernasconi D, Viani A, Zárybnická L, et al.. Phosphate-based geopolymer: Influence of municipal solid waste fly ash introduction on structure and compressive strength. Ceramics International, 2023, 49(13): 22149-22159, J]

[[42]] Ranjbar N, Mehrali M, Alengaram U J, et al.. Compressive strength and microstructural analysis of fly ash/palm oil fuel ash based geopolymer mortar under elevated temperatures. Construction and Building Materials, 2014, 65: 114-121, J]

[[43]] Zeng Y-l, Duan N, Fu C-p, et al.. Preparation and characterization of tungsten tailing-based geopolymers. Ceramics International, 2023, 49(13): 22043-22053, J]

[[44]] Reed B P, Marchesini S, Chemello G, et al.. The influence of sample preparation on XPS quantification of oxygen-functionalised graphene nanoplatelets. Carbon, 2023, 211: 118054, J]

[[45]] Dalby K N, Nesbitt H W, Zakaznova-Herzog V P, et al.. Resolution of bridging oxygen signals from O 1s spectra of silicate glasses using XPS: Implications for O and Si speciation. Geochimica et Cosmochimica Acta, 2007, 71(17): 4297-4313, J]

[[46]] Okewale I A, Grobler H. Assessment of heavy metals in tailings and their implications on human health. Geosystems and Geoenvironment, 2023, 2(4): 100203, J]

[[47]] Liu J, Xie G-m, Wang Z-d, et al.. Synthesis of geopolymer using municipal solid waste incineration fly ash and steel slag: Hydration properties and immobilization of heavy metals. Journal of Environmental Management, 2023, 341: 118053, J]