Phase simulation and experiment of anorthite-diopside glass-ceramics based on stainless steel slag containing chromium
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摘要: 含铬不锈钢渣的大量堆存会导致铬元素的浸出而对环境造成严重的危害，微晶玻璃因其良好的固铬性能和物理性能而具有研究价值。为探究该体系中铬元素的赋存规律，用热力学软件FactSage 7.2对含铬不锈钢渣制备的钙长石-透辉石系微晶玻璃进行了生成相含量的模拟，以此为指导使用含铬不锈钢渣制备了钙长石-透辉石系微晶玻璃，并研究了助熔剂和铬含量对该体系微晶玻璃的结晶和物理性能的影响。结果表明，在模拟计算中，铬元素首先富集在尖晶石相中，最大富集度在10%～20%，多余的铬元素以Cr2O3的形式出现在体系中。在对应的试验探究中，当铬含量达到5%时，体系中的含铬相仍然只有尖晶石相，这使得材料有较好的固铬性能。助熔剂使微晶玻璃具有更高的硬度，铬浸出试验中钙长石-透辉石体系均未检出铬元素。该试验为含铬固体废弃物制备微晶玻璃提供了理论依据。Abstract: Chromium-containing stainless steel slag will lead to the leaching of chromium and environment problems. Glass-ceramics possess excellent chromium fixation and physical properties. In order to explore the occurrence law of chromium in anorthite-diopside system, the phase equilibrium of anorthite-diopside glass ceramics was calculated by using thermodynamic software FactSage 7.2, and the sample were prepared by using chromium-containing stainless steel slag. The effects of flux and chromium content on the crystallization and physical properties of the system glass ceramics were studied. The samples were prepared by one-step method with simultaneous nucleation and crystallization. The results show that in the simulation calculation, chromium is first enriched in the spinel phase, and the excess chromium appears in the system in the form of Cr2O3. In the corresponding experimental exploration, when the chromium content reaches 5%, the chromium-containing phase in the system is still only spinel phase, which makes the material have better chromium fixation properties. The flux endows glass-ceramics with higher hardness. Chromium is detected in anorthite-diopside system in toxic leaching experiment. The experiment provides a theoretical basis for the preparation of glass-ceramics from chromium-containing solid waste.
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图 1 用FaceSage 7.2计算的钙长石-透辉石体系生成相的摩尔量
Figure 1. Molar amount of phase formed in anorthite-diopside system by using FactSage 7.2
图 2 用FaceSage 7.2计算的不同铬含量的生成相的摩尔量
Figure 2. Molar amount of formed phase with different chromium content by using FactSage 7.2
图 3 1400 ℃时生成相中含铬相的变化
Figure 3. Chromium-containing phase variation in product at 1400 ℃
图 4 不同原料制备的微晶玻璃XRD检测结果
Figure 4. XRD results of glass-ceramics prepared from different raw materials
图 6 添加复合助熔剂的微晶玻璃微观形貌,b为a的局部放大图
Figure 6. SEM of glass-ceramics with composite flux, b is the enlarged view of a
图 7 不同铬含量制备的微晶玻璃XRD检测结果
Figure 7. XRD results of glass-ceramics prepared with different chromium content
图 8 不同铬含量微晶玻璃的微观形貌
Figure 8. SEM of glass-ceramics with different chromium content, a: 0.6%, b: 2%, c: 4%, d: 5%
（a）0.6%；（b）2%；（c）4%；（d）5%
图 9 铬含量对样品硬度及耐酸碱的影响
Figure 9. Effects of chromium content on hardness and corrosion resistance of samples
表 1 主要原材料的化学组成
Table 1. Chemical composition of main raw materials
成分 EAF/% 混合钢渣/% CaO 51.9213 22.1288 SiO2 28.4218 47.4188 MgO 5.8954 7.9302 Al2O3 3.0794 20.153 Cr2O3 1.4192 0.6048 Fe2O3 3.227 1.3753 MnO 0.976 0.416 
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表 2 助熔剂对样品硬度及耐腐蚀性的影响
Table 2. Effect of flux on hardness and corrosion resistance of samples
原料 硬度(HV) 失重率/% 酸性环境 碱性环境 混合钢渣 594.3 2.97 1 助熔剂-混合钢渣 3049 0.667 0.446
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表 3 铬浸出试验ICP-OES测试结果
Table 3. ICP-OES results of chromium leaching
样品 Cr/ (mg·L−1) EAF钢渣 0.311 混合钢渣 未检出 助熔剂-混合钢渣 未检出 Cr-2% 未检出 Cr-3% 未检出 Cr-4% 未检出 Cr-5% 未检出
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