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摘要:
某大水型金属矿山帷幕注浆工程中应用的黏土-水泥浆液水化反应后的pH值高达13，表现为强碱性，对地下水及地表水构成了潜在污染风险。为探究低碱性外加剂对该矿山水害防治帷幕注浆工程中黏土-水泥浆液性能的调控机制，采用正交试验设计，系统分析了不同配比条件下浆液的流变特性，包括流动性、泵送性能、凝结时间及pH值的变化规律。通过分别引入磷石膏、粉煤灰及降碱外加剂（substance of Jin Pin，SJP），探讨不同材料在降低浆液碱性方面的有效性。试验结果显示：磷石膏能够将浆液pH值有效降低至11，同时延长凝结时间；粉煤灰虽在降低浆液碱度方面效果有限，却改善了浆液的泵送性能并缩短了泵送期限；SJP外掺剂在降低pH值和延长泵送期方面表现突出，当掺量由2.5%增加至3.5%时，浆液pH值显著降低至8。基于试验数据，优化了SJP外掺剂-粉质黏土-磷石膏-水泥配方，并通过正交试验确定了最优配比：复合酸式盐0.5%、硫铝酸盐1.5%、磷石膏10.0%、黏土50.0%。该优化配方制备的浆液pH值降低至10，流动度保持在18～23 cm，泵送期延长至100～220 min，充分满足工程应用需求。研究结果可为帷幕注浆工程中通过控制浆液碱性减少环境污染提供了科学依据。
Abstract:To investigate the regulatory mechanisms of low-alkalinity admixtures on the performance of clay-cement slurry in mine water hazard prevention and curtain grouting engineering, this study employed an orthogonal experimental design. The rheological properties of the slurry, including flowability, pumpability, setting time, and pH evolution, were systematically analyzed under varying mix conditions. By introducing phosphogypsum, fly ash, and the SJP admixture, the effectiveness of these materials in reducing the alkalinity of the slurry was evaluated. The results reveal that phosphogypsum effectively reduced the pH to 11 and prolonged extending the setting time. Although fly ash showed limited efficacy in alkalinity reduction, it significantly enhanced the pumpability of the slurry and shortened the pumping period. The SJP admixture demonstrates outstanding performance in both pH reduction and pumpability extension, with the pH decreasing notably to 8 when the dosage is increased from 2.5% to 3.5%. Based on experimental data, an optimized formulation of the SJP admixture, clay, phosphogypsum, and cement (CCAS) is developed. Orthogonal tests identify the optimal proportions as follows: composite acid salt 0.5%, calcium sulfoaluminate 1.5%, phosphogypsum 10.0%, and clay 50.0%. The optimized slurry achieves a significant reduction in pH to 10, maintains a flowability of 18–23 cm, and extends the pumpability window to 100–220 minutes, fully meeting the engineering application requirements. This study provides a scientific basis for controlling slurry alkalinity in curtain grouting projects, thereby mitigating environmental pollution.
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表 1 磷石膏化学成分
Table 1. Chemical composition of phosphogypsum
化学成分 CaO SiO2 Al2O3 Fe2O3 MgO 硫酸盐 P2O5 氟化物 质量分数/% 49.06 5.84 0.60 0.41 0.49 42.65 0.82 0.13 
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表 2 粉煤灰主要化学成分
Table 2. Main chemical composition of fly ash
化学成分 SiO2 Al2O3 Fe2O3 CaO MgO 其他 质量分数/% 54.18 22.35 12.36 0.40 0.06 10.65
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表 3 方案一试验配比及结果
Table 3. Results of the proportioning test case 1
试样
编号浆液组成 可泵期/min pH值 黏土/g 水泥/g 磷石膏质量占比/% 水/g 1 500 500 5% 1000 12 12.0 2 500 500 10% 1000 18 12.0 3 500 500 20% 1000 25 11.5 4 500 500 30% 1000 40 11.0 5 500 500 40% 1000 50 11.0 注：磷石膏质量占比为磷石膏占黏土和水泥总质量的百分比。
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表 4 方案二试验配比及结果
Table 4. Results of the proportioning test case 2
试样
编号浆液组成 可泵期 pH值 黏土/g 水泥/g 粉煤灰质量占比/% 水/g 1 500 500 5% 1000 20 min 12.5 2 500 500 10% 1000 22 min 12.5 3 500 500 20% 1000 25 min 12.5 4 500 500 30% 1000 20 min 12.5 5 500 500 40% 1000 19 min 12.0 注：粉煤灰质量占比为粉煤灰占黏土和水泥总质量的百分比。
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表 5 方案三配比试验结果表
Table 5. Results of the proportioning test case 3
试样
编号浆液组成 可泵期
/minpH值 SJP
1#/%SJP
2#/%黏土
/g水泥
/g磷石膏
/%水/g 1 0.5 2.0 300 500 10 1000 20 11.0 2 1.0 2.0 300 500 10 1000 40 10.0 3 1.5 1.5 300 500 10 1000 60 8.6 4 2.0 1.5 300 500 10 1000 75 8.2 5 2.0 1.0 500 500 5 1000 90 8.2 6 2.0 0.8 500 500 5 1000 105 8.0 注：外掺剂加量为固体总重的百分比，磷石膏为黏土和水泥总重的百分比。
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表 6 因素水平表
Table 6. Factor level
因素 A
1#/%B
2#/%C
磷石膏/%D
黏土%1 0.3 1.0 10 50 2 0.5 1.5 13 75 3 0.7 2.0 15 100 注：浆液水灰比固定为0.7，黏土质量占比为水泥质量的百分比，磷石膏质量占比为黏土和水泥总质量的百分比，外掺剂质量占比为固体总质量的百分比。
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表 7 正交试验表
Table 7. Orthogonal test
序号 A B C D 性能指标 流动度/cm 可泵期/min pH值 初凝时间/min 1 1 1 1 1 23 100 10.0 225 2 1 2 2 2 22 160 10.5 220 3 1 3 3 3 20 220 10.8 270 4 2 1 2 3 22 247 10.0 420 5 2 2 3 1 23 225 10.0 290 6 2 3 1 2 19 290 10.9 330 7 3 1 3 2 19 210 10.1 359 8 3 2 1 3 18 180 10.1 260 9 3 3 2 1 22 235 10.0 386 流动度 K1 65 64 60 68 K2 64 63 66 60 K3 59 61 62 60 极差 6 3 6 8 主次 D>A=B>C 优 A1B1C2D1 可泵期 K1 480 557 570 560 K2 762 565 642 660 K3 628 745 625 647 极差 282 188 172 100 主次 A>B>C>D 优 A1B1C1D1 pH K1 31.3 30.1 31.0 30.0 K2 30.9 30.6 30.5 30.5 K3 30.2 31.7 30.9 30.9 极差 1.1 1.6 0.5 0.9 主次 B>A>D>C 优 A3B1C1D1 初凝 K1 715 1004 815 901 K2 1040 770 1026 909 K3 1005 986 919 950 极差 325 234 211 49 主次 A>B>C>D 优 A1B2C1D1
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表 8 优化后各性能参数表
Table 8. Performance parameters after optimization
测试项目 流动度/cm 可泵期/min 初凝时间/min pH值 取值 22 256 312 10
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表 9 岩芯抗压强度结果表
Table 9. Core compressive strength results
序号 直径/mm 高度/mm 抗压强度/MPa 1 61 90 20.40 2 60 101 26.10 3 59 101 28.00 4 62 101 23.30 5 62 103 20.20 6 62 102 25.80
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