Effect of calcination process and calcium-silica ratio on the composition and properties of hydraulic lime
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摘要: 煅烧工艺、原料钙硅比是影响天然水硬性石灰(NHL)矿物组成及性能的关键因素。本文以不同化学组成泥质石灰石尾矿为原料，采用不同煅烧工艺制备了NHL。采用正交试验与单因素试验相结合的方式对所制备NHL的矿物组成及抗压强度进行研究，分析了煅烧工艺与钙硅比对其性能的影响规律。研究结果表明：随着煅烧温度升高，NHL中气硬性矿物CaO含量减少，水硬性矿物硅酸二钙(Ca2SiO4，C2S)含量增加；煅烧温度对NHL的矿物组成及抗压强度影响最为显著，保温时间与升温速率次之；在煅烧温度1 000~1 100 ℃范围内，利用给定的泥质石灰石尾矿制备的天然水硬性石灰满足NHL2、NHL3.5强度等级要求；当钙硅比在3.55~6.76范围内，NHL抗压强度随钙硅比的增大先降低后升高，而CaO含量呈增大趋势。Abstract: The calcination process and the ratio of to calcium to silicon in raw materials are the key factors affecting the mineral composition and properties of natural water hard lime(NHL). This study prepared NHL was by different calcination processes using argillaceous limestone tailings with different chemical compositions as raw materials. This paper studied the mineral composition and compressive strength of the prepared NHL by a combination of orthogonal and single-factor tests, and analyzed the effect of calcination process and calcium-silica ratio on its performance. Results showed that: ① With the increase of calcination temperature, the content of CaO in NHL decreased, and the content of dicalcium silicate(Ca2SiO4, C2S)increased in NHL. ② Calcination temperature had the most significant effect on the mineral composition and compressive strength of NHL, followed by holding time and heating rate. ③ In the calcination temperature range of 1 000~1 100 ℃, the natural hydrostatic lime prepared by the given argillaceous limestone tailings meets the requirements of NHL2 and NHL3.5 strength grades. ④ When the calcium-silicon ratio is in the range of 3.55~6.76, the compressive strength of NHL decreases and then increases with the increase of calcium-silicon ratio, while the CaO content shows continuous increases.
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图 1 不同煅烧工艺下NHL熟料的矿物组成XRD图谱
Figure 1. XRD patterns of mineral composition of NHL clinker under different calcination processes
图 2 煅烧工艺对NHL熟料中CaO质量分数及抗压强度的影响显著性分析结果
Figure 2. Results of significance analysis on the effect of calcination process on CaO content and compressive strength in NHL clinker
图 3 不同钙硅比下NHL熟料的XRD图谱
Figure 3. XRD patterns of NHL clinker at different calcium to silicon ratios
图 4 不同钙硅比下NHL熟料中CaO的质量分数
Figure 4. Content of CaO in NHL clinker at different calcium to silicon ratios
图 5 不同钙硅比下NHL的抗压强度
Figure 5. Compressive strength of NHL at different calcium to silicon ratios
图 6 NHL抗压强度与钙硅比的关系
Figure 6. Relationship between NHL compressive strength and calcium to silicon ratios
表 1 泥质石灰石尾矿1号、2号的主要化学组成
Table 1. Main chemical composition of limestone tailings No.1 and No.2
% 成分 CaO SiO2 Al2O3 Fe2O3 MgO K2O TiO2 SO3 其他 泥质石灰石尾矿1号 67.44 20.38 4.4 1.9 1.82 1.24 0.29 0.08 2.45 泥质石灰石尾矿2号 75.27 11.93 5.67 2.61 1.58 1.23 0.39 0.58 0.74 
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表 2 煅烧工艺对NHL熟料中CaO质量分数及抗压强度的影响
Table 2. Effect of calcination process on CaO content and compressive strength in NHL clinker
编号 因素A 因素B 因素C CaO质量分数/% 强度/MPa 水平 参数 水平 参数 水平 参数 7 d 14 d 28 d 1 1 5 1 30 1 1 000 56.27 0.55 1.28 3.38 2 1 5 2 60 2 1 100 42.06 0.71 1.67 4.44 3 1 5 3 120 3 1 200 19.06 0.57 0.92 1.24 4 1 5 4 180 4 1 250 2.59 0.15 0.30 0.45 5 2 10 1 30 2 1 100 47.85 0.86 1.32 3.51 6 2 10 2 60 1 1 000 56.01 0.70 1.41 3.72 7 2 10 3 120 4 1 250 2.91 0.16 0.31 0.46 8 2 10 4 180 3 1 200 15.28 0.34 0.61 0.83 9 3 15 1 30 3 1 200 30.13 0.64 0.85 1.57 10 3 15 2 60 4 1 250 5.02 0.30 0.66 0.98 11 3 15 3 120 1 1 000 51.40 0.65 1.31 3.46 12 3 15 4 180 2 1 100 37.66 0.86 1.31 3.48 13 4 20 1 30 4 1 250 9.63 0.35 0.61 0.91 14 4 20 2 60 3 1 200 21.07 0.76 0.97 1.14 15 4 20 3 120 2 1 100 42.77 0.63 1.10 2.92 16 4 20 4 180 1 1 000 32.74 0.51 1.03 2.32
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表 3 NHL分类与技术指标要求
Table 3. NHL classification and technical specifics
等级 Ca(OH)2质量分数/% CaO质量分数/% 7 d抗压强度/MPa 28 d抗压强度/MPa NHL2 ≥35 ≥29 — ≥2~≤7 NHL3.5 ≥25 ≥20 — ≥3.5~≤10 NHL5 ≥15 ≥12 ≥2 ≥5~≤15
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表 4 不同强度数据的线性回归分析结果
Table 4. Results of linear regression analysis for different intensity
强度 回归系数(B) R2 显著性影响 VIF 28 d 常量 16.069 0.760 0.000 1 煅烧温度 -0.011 0.000 1 保温时间 -0.028 0.168 1 升温速率 -0.005 0.410 1 14 d 常量 4.869 0.714 0.000 1 煅烧温度 -0.003 0.000 1 保温时间 -0.002 0.094 1 升温速率 -0.004 0.682 1 7 d 常量 2.068 0.431 0.000 1 煅烧温度 -0.001 0.022 1 保温时间 -0.001 0.228 1 升温速率 0.006 0.496 1
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表 5 不同钙硅比NHL生料的原料配比
Table 5. Ratios of NHL raw materials with different calcium to silicon ratios
Level 石灰石尾矿 比例 钙硅比 M1 1号∶2号 1∶0 3.55 M2 1号∶2号 2∶1 4.26 M3 1号∶2号 1∶1 4.73 M4 1号∶2号 1∶2 5.29 M5 1号∶2号 0∶1 6.76
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