Preparation technology and mechanism of cementitious material based on solid waste phosphogypsum
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摘要: 大量堆积的工业固废磷石膏对环境造成了严重污染，同时，传统高能耗的水泥产业与实现“双碳”目标的矛盾日渐突出。已有研究表明，基于磷石膏制备的胶凝材料可以部分替代普通硅酸盐水泥，但使用未经处理的原材料时其工作与力学性能较差。本文主要利用原状磷石膏、矿渣、钢渣和石灰石等常见的工业固废材料，制备绿色高强的磷石膏基胶凝材料。研究结果表明，内掺0.5wt%植物蛋白与胶凝体系中的Ca2+生成螯合物，形成配位化合物覆盖在石膏晶核表面，不仅延缓了胶凝材料的凝结时间，增大了水化反应程度，也提高了其力学性能。通过微观及成分分析表明，磷石膏在胶凝材料中主要作为填充物质，矿渣在钢渣的碱激发作用下发生水化反应，且石灰石在促进水化反应的同时改善了浆体孔结构；基于原状固废磷石膏，采用m磷石膏∶m矿渣∶m钢渣∶m石灰石=0.45∶0.35∶0.1∶0.1配合比制备出的胶砂试件，其28天抗折强度为7.0 MPa、抗压强度为39.1 MPa，软化系数为0.91，接近P·O 42.5级别普通硅酸盐水泥性能。Abstract: A large amount of industrial solid waste phosphogypsum has caused serious pollution to the environment. At the same time, the contradiction between the traditional cement industry with high energy consumption and the realization of the "double carbon" target has become increasingly prominent. Some studies have shown that the cementitious material based on phosphogypsum can replace part of ordinary Portland cement, but its working and mechanical properties are poor when using raw materials without treatment. In this paper, the green and high strength phosphogypsum based cementitious materials were prepared by using common industrial solid wastes such as original phosphogypsum, slag, steel slag and limestone. The results show that chelates are formed by mixing 0.5wt% plant protein with Ca2+ in the gelling system to produce a coordination compound covering the surface of gypsum nucleus, which not only delays the setting time of the gelling material, promotes the hydration reaction degree, but also improves its mechanical properties. The microstructure and composition analysis show that phosphogypsum is mainly used as a filler in the cementitious material, the slag is activated by the alkali of steel slag, and the limestone promotes the hydration reaction while providing Ca2+. Based on the original solid waste phosphogypsum, using the mixture ratio of mphosphogypsum∶mslag∶msteel slag∶mlimestone = 0.45∶0.35∶0.1∶0.1, 28 days flexural strength of mortar specimen is 7.0 MPa, compressive strength is 39.1 MPa, and softening coefficient is 0.91, which is very close to the performance of P·O 42.5 grade ordinary Portland cement.
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图 2 磷石膏基胶凝材料实验过程
Figure 2. Experimental process of phosphogypsum based cementitious materials
AFt—Ettringite; C-S-H—Calcium silicate hydrate
图 3 不同预处理方式下磷石膏基胶凝材料安定性测试结果
Figure 3. Test results of stability of phosphogypsum based cementitious material under different pretreatment methods
图 4 不同预处理方式下磷石膏基胶凝材料的凝结时间
Figure 4. Setting time of phosphogypsum based cementitious materials under different pretreatment methods
图 5 预处理对磷石膏基胶凝材料力学性能的影响
Figure 5. Effect of pretreatment on mechanical properties of phosphogypsum based cementitious materials
图 6 配合比对磷石膏基胶凝材料力学性能的影响
Figure 6. Effect of mix ratio on mechanical properties of phosphogypsum based cementitious materials
图 7 最优配比下磷石膏基胶凝材料吸水率和软化系数随时间的变化
Figure 7. Changes of water absorption and softening coefficient of phosphogypsum based cementing material with time under optimal ratio
图 8 不同VP用量的磷石膏基胶凝材料水化产物SEM图像
Figure 8. SEM images of hydration products for phosphogypsum based cementitious materials with different VP dosages
图 9 磷石膏基胶凝体系水化反应示意图：((a)~(c)) 不掺VP的水化反应过程；((d), (e)) 掺VP的水化反应过程
Figure 9. Schematic diagram of hydration reaction of phosphogypsum based cementitious system: ((a)-(c)) Hydration reaction process without VP mixing; ((d), (e)) Hydration reaction process with VP mixing
SS—Steel slag; LS—Limestone
图 10 不同龄期下磷石膏基胶凝材料水化产物的SEM图像((a)~(c))和EDS能谱((d)~(f))
Figure 10. SEM images ((a)-(c)) and EDS spectra ((d)-(f)) of hydration products for phosphogypsum based cementitious materials at different ages
表 1 原材料化学成分
Table 1. Chemical composition of raw materials
Material LOI CaO
/wt%SiO2
/wt%Al2O3
/wt%SO3
/wt%Fe2O3
/wt%MgO
/wt%P2O5
/wt%F
/wt%Others
/wt%PG 11.97 34.52 3.21 1.09 47.30 0.31 0.06 1.10 0.20 0.24 Slag 3.36 34.00 34.50 17.70 1.64 1.03 6.01 — — 1.76 Steel slag 5.05 29.12 14.32 3.80 6.05 31.24 9.30 — — 1.12 Limestone 40.91 51.36 4.10 1.24 — 0.30 0.72 — — 1.37 Notes：PG—Phosphogypsum; LOI—Loss on ignition. 
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表 2 磷石膏基胶凝材料试验参数设计
Table 2. Design of experimental parameters of phosphogypsum based cementitious material
No. Mass composition/wt% Anhydrous sodium citrate Steel slag (solution) PG Slag Steel slag Limestone VP Purpose BG-P45 — — 45 35 10 10 — Effect of pretreatment method SL-P45 — 2 45 35 10 10 — AC-P45 4 — 45 35 10 10 — VP−-P45 — — 45 35 10 10 0.25 VP-P45 — — 45 35 10 10 0.5 VP+-P45 — — 45 35 10 10 1 VP-P35 — — 35 45 10 10 0.5 Effect of mix ratio VP-P55 — — 55 25 10 10 0.5 Notes: For example, BG-P45 stands for the benchmark group without pretreatment and PG accounts for 45% the quality of the cementitious material; AC—Anhydrous sodium citrate; SL—Steel slag; VP+, VP and VP− represents different dosage of vegetable protein as 1wt%, 0.5wt% and 0.25wt%, respectively.
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表 3 磷石膏预处理方式对胶凝材料性能的影响
Table 3. Effect of phosphogypsum pretreatment methods on properties of cementitious materials
Group Stability Initial setting
time/minFinal setting
time/minCompressive
strength/MPaFlexural strength/MPa 3 d 7 d 28 d 3 d 7 d 28 d BG-P45 Qualified 164 202 1.9 7.7 18.5 0.9 2.1 4.4 SL-P45 Qualified 95 132 3.4 8.6 25.5 2.2 3.5 5.5 AC-P45 Qualified 195 260 3.5 8.2 27.2 2.5 3.7 6.9 VP−-P45 Qualified 243 307 5.4 8.5 27.3 1.8 2.3 5.2 VP-P45 Qualified 295 366 7.6 14.1 39.1 2.3 3.3 7.0 VP+-P45 Qualified 319 390 6.7 10.8 32.4 2.1 2.7 6.0
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