Curing performance of alkali-activated cement–phosphorous slag and its compatibility with sulfur tailings
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摘要: 基于磷渣材料水化特性和礦山充填應用條件，研究堿激發水泥?磷渣共同作為膠凝材料（CPCM）膠結含硫尾砂的可行性。選取生石灰、NaOH、Na2SiO3作為激發劑，開展CPCM固化性能試驗，并評價CPCM與含硫尾砂相容性。研究結果表明：磷渣摻量為水泥的100%、生石灰為3%時，CPCM終凝時間300 min，28 d抗壓強度40.6 MPa，基本可等量替代P.O 42.5水泥應用于礦山嗣后充填。Na2SiO3摻量4%時，CPCM終凝時間比水泥縮短39.3%，7 d強度提高31.1%。與水泥相比，CPCM使充填體凝結時間縮短8 h左右，且固化28 d后強度未出現劣化，表明CPCM與含硫尾砂相容性好。X射線衍射、掃描電鏡和電子能譜分析表明，CPCM水化產物主要為Ca(OH)2和C?S?H。磷渣不斷水化，導致Ca(OH)2含量下降，逐漸形成致密的低Ca/Si摩爾比C?S?H，這不僅保證了CPCM后期強度增加，而且避免了充填體強度劣化。Abstract: Phosphorus slag (PS) is an industrial waste discharged during the refining of yellow phosphorus by a high-temperature electric furnace. The slag is generally deposited on the surface in situ, and this uses up considerable areas of land and causes environmental pollution problems. The glass phase content in electric furnace PS is over 90%, indicating that the PS has potential cementitious property. As a cement admixture, PS has a retarding effect on cement, thus, its application to cement has become less adopted. Based on the hydration characteristics of PS and the application conditions of mine filling, the feasibility of alkali-activated cement–PS used as cementitious material (CPCM) to cement sulfur tailings was studied. Quicklime, NaOH, and Na2SiO3 were used as the activators to investigate the CPCM curing performance in a laboratory, and the compatibility of CPCM with sulfur tailings was evaluated. The results show that when the PS-to-cement mole ratio is 1∶1, quicklime is 3% of PS, the final setting time of CPCM is 300 min, and the CPCM strength for 28 days is 40.6 MPa, indicating that the material can replace P.O 42.5 cement in the subsequent filling process. When the Na2SiO3 is 4% of PS, the final setting time of CPCM is 39.3% less than that of cement, and its strength for 7 days is 31.1% higher than that of cement. Compared with cement, CPCM shortens the setting time of backfill by 8 hours, and its strength does not deteriorate after curing for 28 days. Therefore, CPCM is suitable for cementing sulfur tailings. X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS) analyses show that the CPCM hydration products are mainly Ca(OH)2 and C?S?H. Moreover, the PS hydration resulted in a decrease in the Ca(OH)2 content, and a compact C?S?H gel with a low Ca/Si mole ratio is formed. This not only improves the later strength of CPCM but also prevents the strength deterioration of the backfill.
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Key words:
- phosphorus slag /
- alkali activators /
- early activity /
- sulfur tailings /
- mine filling
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圖 3 磷渣摻量對CPCM固化性能影響。（a）凝結時間；（b）抗壓強度
Figure 3. Effect of PS mass fraction on the cementitious material (CPCM) hardening properties: (a) setting time; (b) strength
圖 4 生石灰摻量對CPCM固化性能影響。（a）凝結時間；（b）抗壓強度
Figure 4. Effect of quicklime mass fraction on the CPCM hardening properties: (a) setting time; (b) strength
圖 5 NaOH摻量對CPCM固化性能影響。（a）凝結時間；（b）抗壓強度
Figure 5. Effect of NaOH mass fraction on the CPCM hardening properties: (a) setting time; (b) strength
圖 6 Na2SiO3摻量對CPCM固化性能影響。（a）凝結時間；（b）抗壓強度
Figure 6. Effect of Na2SiO3 mass fraction on the CPCM hardening properties: (a) setting time; (b) strength
圖 7 CPCM類型對CPTB固化性能影響。（a）凝結時間；（b）抗壓強度
Figure 7. Effect of CPCM type on the CPTB hardening properties: (a) setting time; (b) strength
圖 8 水化產物X射線衍射圖譜。（a）CPCM；（b）CPTB
Figure 8. XRD patterns of hydration products: (a) CPCM; (b) CPTB
圖 9 水化產物掃描電鏡圖。（a）CPD-28 d；（b）DL3-28 d；（c）DN4-7 d；（d）CPTB-1#-90 d；（e）CPTB-2#-90 d；（f）CPTB-3#-90d
Figure 9. SEM images of hydration products: (a) CPD-28 d; (b) DL3-28 d; (c) DN4-7 d; (d) CPTB-1#-90 d; (e) CPTB-2#-90 d; (f) CPTB-3#-90d
表 1 水泥、全尾砂和磷渣化學成分
Table 1. Chemical compositions of cement, tailings, and phosphorus slag
Raw materials Mass fraction/% CaO SiO2 Al2O3 P2O5 Fe2O3 MgO Cement 62.35 20.18 5.22 0.48 3.27 2.16 Tailings 6.95 17.26 10.03 — 16.34 0.18 Phosphorus slag (PS) 43.18 37.37 5.78 3.93 0.25 2.57 
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表 2 CPCM配合比設計
Table 2. Design of CPCM mix ratio
Name of mix ratio Mass fraction of phosphorus slag /% Mass fraction of activators /% Type of activators CPO 0 0 Pure cement paste CPA 25 0 CPB 50 CPC 75 CPD 100 DL3 100 3 Quicklime DL6 6 DL9 9 DH2 100 2 NaOH (by Na2O mass fraction) DH4 4 DH6 6 DN2 100 2 Na2SiO3 (by Na2O mass fraction) DN4 4 DN6 6
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中文字幕在线观看表 3 CPTB配合比設計
Table 3. Design of CPTB mix ratio
Name of filing body Type of binders Mass fraction of paste/% Binder sand ratio CPTB?1# CPO 76 1∶12 CPTB?2# DL3 76 1∶12 CPTB?3# DN4 76 1∶12
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