Step optimization of a solid waste-based binder for backfill and a study on hydration and cementation mechanism
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摘要: 充填體強度對安全高效采礦至關重要，而膠凝材料是獲得高強度充填體的關鍵。本文以工業固廢為原料，首先借助D-optimal設計方法通過建立強度回歸模型和因素影響分析得到礦渣激發劑最佳配比，然后通過礦渣摻量優化試驗獲得最佳礦渣摻量，進而獲得膠凝材料完整配比；并以水泥為參照，借助X射線衍射儀和掃描電鏡從水化產物和充填體微觀結構揭示充填體強度形成機制。結果表明：（1）激發劑各組分對礦渣敏感順序為：氫氧化鈉﹥熟石灰﹥脫硫石膏﹥硫酸鈉，且相互之間存在不同程度的交互作用；（2）在最佳質量配比（礦渣85.00%，熟石灰8.03%，硫酸鈉3.96%，脫硫石膏1.85%，氫氧化鈉1.16%）下，可獲得超過單一水泥3.5倍的早期(1~3 d)強度和2倍的后期(7~28 d)強度；（3）高強度充填體的形成主要與水化產物鈣礬石（AFt）和C–S–H有關，鈣礬石在早期快速成核與生長，形成有效物理填充作用是形成較高早期強度的主要原因，后期強度則得益于不斷累積的C–S–H的包裹黏結作用，使充填體結構進一步致密化。使用該固廢基膠凝材料有助于礦山安全采礦；工業固廢質量占比86.85%，協同解決了尾砂、礦渣、脫硫石膏等固廢；D-optimal設計方法可用于激發劑等多物料混合物的配比設計和因素作用分析。
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關鍵詞:
- 尾砂膠結充填 /
- 膠凝材料 /
- D-optimal混料設計方法 /
- 水化 /
- 抗壓強度
Abstract: The key to obtaining high-strength backfill is the cementing material used for backfilling. Therefore, to prepare a new slag-based binder for cemented tailings backfill, hydrated lime, desulfurized gypsum, sodium sulfate, and sodium hydroxide were selected as slag activators. Firstly, the D-optimal mixture design method was used to develop the strength regression model, analyze the influence of hydrated lime, desulfurized gypsum, sodium sulfate, and sodium hydroxide on the strength, and determine the best ratio of slag activator. Secondly, after optimizing the slag content, the optimum proportion of the binder was obtained. Lastly, X-ray diffraction and scanning electron microscopy were used to study the internal mechanism of the hydration products of the slag-based binder, the microstructure of backfill, and strength formation. The results show that the D-optimal mixture design method is a good method of obtaining the formula of the mixture with a less experimental amount. The sensitivity order to slag is sodium hydroxide > hydrated lime > desulfurized gypsum > sodium sulfate, and there are different degrees of interaction, so the weighing accuracy should be considered when batching. At the optimum mass ratio of binder (slag 85.00%, slaked lime 8.03%, sodium sulfate 3.96%, desulfurized gypsum 1.85%, and sodium hydroxide 1.16%), the early strength (1–3 d) is 3.5 times higher than that of cement, and the late strength (7–28 d) is at least two times higher than that of cement. The increased strength of hardened backfill cemented is closely related to ettringite (AFt) and C–S–H, the two primary hydration products of the new slag-based binder. During the early stages of hydration, a large amount of AFt rapidly nucleated on the surface of the slag, the distance between the tailing particles provided plenty of space for ettringite growth, and its long prismatic structure continuously extended into the intergranular pores. The rapid formation of early strength of backfill is primarily because of the physical filling effect of ettringite. In the later stage, the strength of the backfill is primarily attributed to the wrapping and bonding effect of C–S–H, which further optimizes the compact structure of the backfill. The high-strength backfill can be obtained using the new slag-based cementitious material, which is of great significance for safe and efficient mining. The slag-based binder that contains 86.94% (mass fraction) of industrial solid waste helps solve the problem of desulfurized gypsum of coal-fired power plants and mine tailings. Additionally, the D-optimal mixture design proved to be an effective method for designing and optimizing the ratio of multicomponent materials, such as binders and activator components.-
Key words:
- cemented tailings backfill /
- binder /
- D-optimal mixing design method /
- hydration /
- compressive strength
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圖 1 尾砂、礦渣、脫硫石膏、熟石灰和OPC的粒徑分布
Figure 1. Particle size distribution of tailings, slag, desulfurized gypsum, hydrated lime, and cement
圖 2 主要固體粉料的XRD譜圖。(a) 尾砂；(b) 礦渣；(c) OPC
Figure 2. XRD patterns of main solid materials: (a) tailings; (b) slag; (c) OPC
圖 5 熟石灰、硫酸鈉、脫硫石膏和氫氧化鈉對充填體強度的影響
Figure 5. Influence of hydrated lime, sodium sulfate, desulfurized gypsum, and sodium hydroxide on the strength of cemented backfill
圖 7 礦渣摻量對尾砂充填體強度的影響
Figure 7. Effect of slag dosage on strength of cemented tailings backfill
圖 8 使用OPC和新型膠凝材料制備充填體的強度對比
Figure 8. Strength comparison between backfill prepared with OPC and new binder
圖 9 礦渣基堿激發膠凝材料（a）和OPC制備（b）凈漿樣品水化3 d和14 d的XRD譜圖（H—氫氧化鈣；E—鈣礬石(AFt)；R—水化硅酸鈣(C–S–H)；Z—針硅鈣石；C—碳酸鈣；Q—石英；G—GaSO4·2H2O；A—鋁酸三鈣; F—鐵鋁酸四鈣；D—硅酸二鈣；B—半水硫酸鈣；T—硅酸三鈣）
Figure 9. XRD patterns of paste sample prepared using a new alkali-activated slag-based binder (a) and cement (b) after hydration for 3 and 14 d (H—Calcium hydroxide; E—Ettringite (AFt); R—Calcium silicate hydrate (C–S–H); Z—Hillebrandite; C—Calcium carbonate; Q—Quartz; G—Gypsum; A—Calcium aluminate; F—Tetracalcium aluminoferrite; D—Dicalcium silicate; B—Hemihydrate gypsum; T—Tricalcium silicate)
圖 10 新型膠凝材料和OPC制備充填體內部微觀形貌對比。(a)新型膠凝材料樣品，養護3 d；(b)新型膠凝材料樣品，養護14 d；(c) OPC樣品，養護3 d；(d) OPC樣品，養護14 d
Figure 10. Comparison of the internal morphology of backfill prepared using the new binder and cement: (a) new binder sample, cured for 3 d; (b) new binder sample, cured for 14 d; (c) cement sample, cured for 3 d; (d) cement sample, cured for 14 d
表 1 固體材料化學組成（質量分數）
Table 1. Chemical compositions of solid materials by mass
% Solid material CaO SiO2 Al2O3 MgO SO3 Na2O TiO2 Fe2O3 K2O MnO P2O5 Tailings 2.72 70.70 15.00 1.10 0.27 3.52 0.15 1.28 4.93 0.04 0.06 Slag 39.80 27.30 14.50 11.40 2.50 — 1.07 0.24 0.27 0.33 0.02 Desulfurized gypsum 41.98 2.86 1.34 2.48 51.03 — — 0.41 0.14 — 0.02 OPC 50.34 24.21 8.94 6.64 4.01 0.86 0.38 2.34 1.21 0.21 0.06 
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表 2 D-optimal設計方案及強度結果
Table 2. Scheme and strength results of D-optimal mixture design
Order Mass fraction / % Mean strength-7 d/MPa Slag A: Hydrated lime B: Sodium sulfate C: Desulfurized gypsum D: Sodium hydroxide 1 60 19.47 14.51 5.00 1.02 1.87 2 60 15.00 19.00 1.00 5.00 1.91 3 60 20.19 12.13 3.16 4.52 2.28 4 60 26.34 5.00 5.00 3.66 2.40 5 60 25.72 10.67 1.00 2.61 2.18 6 60 15.84 14.16 5.00 5.00 2.34 7 60 13.83 20.00 3.34 2.83 2.30 8 60 33.00 5.00 1.00 1.00 1.96 9 60 12.16 17.84 5.00 5.00 2.05 10 60 13.83 20.00 3.34 2.83 2.24 11 60 21.80 16.20 1.00 1.00 2.17 12 60 20.19 12.13 3.16 4.52 2.24 13 60 26.34 5.00 5.00 3.66 2.44 14 60 18.05 19.95 1.00 1.00 2.30 15 60 20.19 12.13 3.16 4.52 2.24 16 60 23.21 10.81 4.98 1.00 2.32 17 60 25.72 10.67 1.00 2.61 2.06 18 60 29.17 7.10 2.73 1.00 2.00 19 60 23.01 8.19 3.80 5.00 2.14 20 60 29.00 5.00 1.00 5.00 1.90
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表 3 方差分析結果
Table 3. Results of variance analysis
Source Sum of squares Degree of freedom Mean square F-value P-value Remark Model 0.5539 13 0.0426 17.41 0.0011 Significant Linear mixture 0.1058 3 0.0353 14.41 0.0038 — AB 0.0006 1 0.0006 0.2461 0.6375 — AC 0.0018 1 0.0018 0.7254 0.4271 — AD 0.0625 1 0.0625 25.52 0.0023 — BC 0.0237 1 0.0237 9.70 0.0207 — BD 0.0501 1 0.0501 20.45 0.0040 — CD 0.0084 1 0.0084 3.42 0.1138 — ABC 0.0528 1 0.0528 21.56 0.0035 — ABD 0.0252 1 0.0252 10.28 0.0185 — ACD 0.0001 1 0.0001 0.0529 0.8257 — BCD 0.0048 1 0.0048 1.98 0.2094 — Residual 0.0147 6 0.0024 — — — Lack of fit 0.0038 1 0.0038 1.76 0.2423 Not significant Corrected total 0.5686 19 — — — —
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表 4 優化組合及其期望值
Table 4. Optimized combination and its expected value
Order Optimized combination/% Predicted value/MPa Expected value/MPa A B C D 1 21.42 10.57 4.92 3.09 3.02 0.865 2 19.77 13.00 4.28 2.96 2.93 0.796 3 24.69 9.00 3.50 2.81 2.86 0.743
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表 5 驗證試驗及其結果
Table 5. Optimized combination and its expected value
Order Optimized combination/% Predicted value/MPa Actual value/MPa Deviation/% A B C D 1 21.42 10.57 4.92 3.09 3.02 2.72 9.93 2 19.77 13.00 4.28 3.09 2.93 2.55 13.00 3 24.69 9.00 3.50 3.09 2.86 2.49 12.87
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