赤泥-磷石膏在配炭配碱条件下的热分析及反应动力学

Thermal analysis and reaction kinetics study of red mud and phosphogypsum mixed solid waste with added carbon and alkali

  • 摘要: 赤泥和磷石膏的大量生成及堆存会带来环境风险,尽管已有协同焙烧利用的研究,但高温反应动力学仍缺乏深入探讨。采用差热-量热分析技术,研究了在添加碳酸钠和焦炭的条件下,赤泥与磷石膏混合物的高温反应特性。结果表明:在低温(<200 ℃)单独焙烧条件下反应活化能为61.72 kJ/mol,加入碳酸钠后反应活化能显著降低至14.09 kJ/mol,并加快反应速率;加入焦炭后,活化能进一步降低至1.58 kJ/mol,反应显著加快,CaSO4分解温度降低。在单独焙烧条件下, 剧烈反应区间主要发生在1 000~1 200 ℃;加入碳酸钠后,反应温度区间显著降低至600~850 ℃,表明碱的加入有效降低了反应所需的温度并加快了反应速率。进一步加入焦炭后,反应的温度区间再次上升至800~1 000 ℃,这表明焦炭的加入促进了反应过程,尽管温度略有升高,但仍处于较低的温度区间,反应仍然较为剧烈。研究揭示了混料焙烧过程主要遵循成核与生长及三维扩散的反应机理。此研究为赤泥与磷石膏的协同利用及工业固废的资源化提供了新的理论依据。

     

    Abstract: Red mud and gypsum are the main solid waste products of the aluminum and phosphate chemical industries. Due to their large-scale generation, storage, and complex chemical composition, they pose potential environmental risks, which have attracted widespread attention. Although there have been some advances in the utilization of red mud and gypsum in co-pyrolysis, there is still a relative lack of research on the reaction mechanisms, especially the high-temperature kinetics of their co-calcination or pyrolysis. Therefore, this study used differential thermal-thermogravimetric analysis to systematically investigate the high-temperature reaction kinetics of the mixed solid waste of red mud and gypsum in the presence of sodium carbonate and charcoal. The experimental results show that under the condition of separate mixing pyrolysis with decomposition temperature lower than 200 ℃, the reaction activation energy of red mud and gypsum is 61.72 kJ/mol. After adding sodium carbonate, the reaction activation energy is significantly reduced to 14.09 kJ/mol, and the reaction rate is accelerated. Further addition of charcoal reduces the reaction activation energy to 1.58 kJ/mol, and the reaction is significantly intensified, with a marked decrease in the decomposition temperature of CaSO4.Under single-component calcination, the most intense reaction occurs in the 1 000-1 200 ℃ range. With the addition of sodium carbonate, the reaction window shifts markedly downward to 600-850 ℃, indicating that the alkali effectively lowers the required temperature and accelerates the reaction rate. Upon further addition of coke, the reaction window rises slightly to 800-1 000 ℃, suggesting that coke promotes the reaction process. Although the temperature increases somewhat, it remains within a relatively lower range and the reaction is still vigorous. In addition, this study reveals that the reaction mechanism of mixing pyrolysis is mainly composed of nucleation and growth and three-dimensional diffusion. These findings provide a new theoretical basis for optimizing the synergistic utilization of red mud and gypsum.

     

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