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矿渣−电石渣胶凝材料的孔隙分形特征及其对重金属吸附的影响

Pore fractal characteristics of granulated blast furnace slag-carbide slag cementitious material and its effect on heavy metal adsorption

  • 摘要: 煤炭长期占据我国能源消费结构的主体地位,因煤炭洗选加工及巷道开拓活动,矿井水中重金属污染问题日益严峻。胶凝材料在治理重金属矿井水方面具有显著优势,其孔隙结构特征及分形特性对吸附性能起着关键作用。为了研究胶凝材料孔隙结构及孔隙分形特征对重金属离子的吸附影响,以矿渣和电石渣制备固废胶凝材料(GCCM),通过XRD、SEM、低温N2吸附/脱附、Cr6+吸附等试验方法和FHH分形模型,开展GCCM水化产物演变、孔隙分形特征及Cr6+吸附性能研究。结果表明:GCCM水化产物以C−(A)−S−H凝胶为主,当n(CaO)/n(SiO2+Al2O3)为0.635时,凝胶网络致密。低温氮气吸附/脱附曲线属IV型并呈现H2型滞后环,以介孔(2~50 nm)为主;GCCM孔隙结构特征存在明显的分形行为,孔隙内部分形维数D2大于孔隙表面分形维数D1,反映C−(A)−S−H凝胶水化产物主导的多级孔隙结构及材料非均质性导致内部空间复杂性更高。分形维数D与抗压强度、比表面积和孔体积正相关,与平均孔径和n(CaO)/n(SiO2+Al2O3)负相关;GCCM对Cr6+的吸附过程符合Langmuir单分子层吸附,D与Cr6+最大吸附量(Qmax)正相关,D1Qmax的影响更显著(R2=0.964),GCCM表面孔隙为重金属的吸附提供了直接接触位点。GCCM的重金属离子浸出浓度满足GB 8978—1996《污水综合排放标准》中Ⅲ类水和GB 20426—2006《煤炭工业污染物排放标准》等多项限值要求。研究为固废基胶凝材料在矿井水重金属治理中的应用提供了分形理论支撑与配比优化依据。

     

    Abstract: Coal has long occupied the main position of energy consumption structure in China. The problem of heavy metal pollution in mine water has become increasingly severe due to washing and processing as well as tunnel development activities. Cementitious materials have significant advantages in the treatment of heavy metal mine water, and their pore structure characteristics and fractal properties play a key role in the adsorption performance. In order to study the adsorption effect of pore structure and pore fractal characteristics of cementitious materials on heavy metal ions, solid waste cementitious materials (GCCM) were prepared from slag and carbide slag. Through experimental methods such as XRD, SEM, low-temperature N2 adsorption/desorption, Cr6+ adsorption, and the FHH fractal model, the evolution of hydration products of GCCM, the characteristics of pore fractals and the adsorption performance of Cr6+ were studied. The results show that the hydration products of GCCM are mainly C−(A)−S−H gel. When the molar ratio of n(CaO)/n(SiO2+Al2O3) is 0.635, the gel network is dense. The adsorption/desorption curve of low-temperature nitrogen belongs to Type IV and presents a hysteresis loop of type H2, mainly mesoporous (2−50 nm). The pore structure characteristics of GCCM show obvious fractal behavior. The partial shape dimension within the pore (D1) is greater than the fractal dimension of the pore surface (D2), reflecting that the multi-level pore structure dominated by the hydration products of C−(A)−S−H gel and the material heterogeneity lead to higher internal spatial complexity. The fractal dimension D is positively correlated with compressive strength, specific surface area and pore volume, and negatively correlated with average pore diameter and n(CaO)/n(SiO2+Al2O3). The adsorption process of Cr6+ by GCCM conforms to the Langmuir monolayer adsorption. D is positively correlated with the maximum adsorption capacity (Qmax) of Cr6+, and D1 has a more significant effect on Qmax (R2=0.964). The surface pores of GCCM provide direct contact sites for the adsorption of heavy metals. The leaching concentration of heavy metal ions in GCCM meets multiple limit requirements such as Class III water in GB 8978—1996 and GB 20426—2006. The research provides fractal theoretical support and proportioning optimization basis for the application of solid waste-based cementitious materials in the treatment of heavy metals in mine water.

     

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