Study on the properties of steel slag used as sulfur fixation agent in coal burning
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摘要: 为研究燃煤固硫过程中钢渣的固硫性能，分析了固硫过程的工艺参数钙硫比、空气流量、炉温、炉内停留时间等单因素对固硫率的影响，并设计正交实验分析各因素对固硫率主次顺序的影响，确定了最优实验参数。使用X射线荧光光谱仪(XRF)分析了灰渣的结渣性和钢渣的固硫效果；应用X射线衍射光谱仪(XRD)表征了钢渣与固硫灰渣的衍射峰，进一步反映了钢渣的固硫性能；采用扫描电镜(SEM)表征了固硫灰渣的显微形貌，比较了钢渣固硫前后的表面结构和微观形貌，验证了其他表征结果的合理性。结果表明，钢渣在900 ℃高温下具有较好的固硫性能，固硫率达到63.17%，加入2%碳酸钠助剂后钢渣的固硫率可以达到70.08%。Abstract: In order to research the sulfur fixation performance of steel slag in the coal-fired sulfur fixation process, the effect of single parameters such as calcium-sulfur ratio, air flow rate, furnace temperature, and furnace residence time on the sulfur fixation efficiency was studied. In addition, orthogonal experiments were constructed to assess the effect of each variable on the main and secondary order of sulfur fixation efficiency, and the ideal experiment design was identified. Utilizing XRF, the slagging features of the ash and the sulfur-fixing effect of the steel slag were analyzed.XRD was utilized to characterize the diffraction peaks of steel slag and sulfur fixation slag, which indicated the steel slag's capacity to fixate sulfur. SEM was used to describe the microscopic morphology of sulfur fixing ash, and the surface structure and microscopic morphology of steel slag before and after sulfur fixing were compared to evaluate the validity of other characterisation results. The results suggest that the slag has a good sulfur fixation capacity at 900 ℃, with a sulfur fixation efficiency of 63.17%, and that the sulfur fixation efficiency of the slag may reach 70.08% when 2% Na2CO3 is added.
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Key words:
- steel slag /
- sulfur fixing agen /
- sulfur fixation rate /
- the process parameters /
- orthogonal experiments
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图 1 钙硫比对钢渣固硫率的影响
Figure 1. Effect of calcium to sulfur molar ratio on sulfur-fixing efficiency of steel slag
图 2 空气流量对钢渣固硫率的影响
Figure 2. Effect of air flow on sulfur-fixing efficiency of steel slag
图 3 管式炉温度对钢渣固硫率的影响
Figure 3. Effect of temperature of tubular furnace on sulfur-fixing efficiency of steel slag
图 4 燃烧时间对固硫率的影响
Figure 4. Effect of combustion time on sulfur-fixing efficiency of steel slag
图 5 固硫灰渣和钢渣的XRD谱
Figure 5. XRD patterns of coal ash and steel slag
1—Fe3O4; 2—Ca2SiO4; 3—Ca3SiO; 4—Ca2Fe2O3; 5—SiO2; 6—Fe2O3; 7—CaSO4
表 1 太原煤的工业分析与热值
Table 1. Analysis of proximate and heating value of Taiyuan coal samples
Mad/% Aad/% Vad/% FCad/% St，ad/% Qb，ad/(MJ·kg-1) 1.380 36.42 25.99 36.26 2.440 20.19 
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表 2 钢渣的化学元素分析
Table 2. Analysis of chemical element in steel slag
% 元素 Ca Fe Si Mg Mn Al P Ti V Cr 含量 30.6 17.7 7.85 2.12 2.66 1.67 0.815 0.838 0.272 0.304 元素 Na Ba K Sr Cl W Ag Zn Nb Zr 含量 0.147 0.107 0.064 0.040 0.030 0.021 0.022 0.018 0.011 0.011
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表 3 正交实验因素和水平
Table 3. Factors and levels of orthogonal experiments
水平 钙硫比(A) 空气流量/(L·min-1)(B) 停留时间/min(C) 炉温/℃(D) 1 1.5 1 10 900 2 2.0 2 15 950 3 2.5 3 20 1 000 4 3.0 4 25 1 050
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表 4 正交实验方案与结果分析
Table 4. Orthogonal experiments plan and experiment results
实验号 A B C D 固硫率/% 1 1 1 1 1 20.88 2 1 2 2 2 27.43 3 1 3 3 3 19.63 4 1 4 4 4 15.29 5 2 1 2 3 26.11 6 2 2 1 4 47.07 7 2 3 4 1 44.34 8 2 4 3 2 39.58 9 3 1 3 4 20.30 10 3 2 4 3 37.70 11 3 3 1 2 42.48 12 3 4 2 1 49.17 13 4 1 4 2 54.36 14 4 2 3 1 60.40 15 4 3 2 4 28.46 16 4 4 1 3 45.97 k1 20.807 30.412 39.100 43.697 k2 39.275 43.150 32.793 40.962 k3 37.412 33.727 34.977 32.352 k4 47.297 37.502 37.922 27.780 极差R 26.490 12.738 6.307 15.910 主次顺序 A＞D＞B＞C 最佳方案 A4B2C1D1 注：ki为平均响应值(本实验中为固硫率)，即相同因素下同一水平的实验响应值的算术平均值；R为相同因素下ki的最大值与最小值的差，R越大，表明因素的水平变化对实验的影响越大。
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表 5 煤灰组成的XRF分析结果
Table 5. XRF analytical results on coal ash
% 灰样 wSiO2 wCaO wSO3 wAl2O3 wFe2O3 wMgO wK2O wTiO2 wNa2O wV2O5 wP2O5 wBaO wZnO A0 52.6 2.15 0.886 30.6 9.20 0.801 1.640 1.29 0.231 0.098 8 0.060 3 0.029 6 0.027 7 A1 40.6 13.0 1.340 23.8 15.10 1.240 1.230 1.36 0.322 0.146 0 0.298 0 0.056 8 0.032 4 A2 34.3 17.7 4.120 20.1 17.6 1.420 0.936 1.21 0.297 0.186 0 0.401 0 0.055 4 0.035 7
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表 6 结渣倾向性判别结果
Table 6. The discriminant results of slagging tendency
判别指数 渣样标号 判断依据 结果 A0 A1 A2 轻微 中等 严重 $ \frac{m_{\mathrm{SiO}_2}}{m_{\mathrm{Al}_2 \mathrm{O}_3}} $ 1.72 1.71 1.71 ＜1.87 1.87~2.65 ＞2.65 不易结渣
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