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氨气还原球团矿的反应行为及机制分析

Reaction behavior and mechanism analysis of ammonia reduction of pellets

  • 摘要: 氨气作为富氢载体,拥有成熟的贸易路线和较低的液化成本,可以直接作为铁矿石的清洁还原剂。现有的研究通过热力学计算、基础试验以及动力学拟合给出了氨还原的热力学参数和反应活化能等数据,但并未明确氨还原的机制。本文通过研究不同温度、不同时间下球团矿还原的反应行为、矿相组成以及微观形貌,进一步结合还原膨胀率变化、热力学分析和动力学拟合结果,得到了氨气还原球团矿的机制。研究结果表明,随着温度从700 ℃增加到900 ℃,还原度达到0.95的时间由93.5 min降低到43.2 min,还原后球团矿中的氮质量分数从0.029%降低到0.019%。动力学拟合结果表明,不同温度下的氨气还原球团矿的机制有所区别,在700 ℃还原时,随着还原的进行,分别由扩散控制、化学反应控制以及形核控制,在900 ℃还原时,均由扩散控制。总体而言,球团矿在氨气条件下还原时,外部主要表现为赤铁矿被氨气还原为磁铁矿,使球团矿发生第1次膨胀,随着反应的进行,金属铁的生成催化了氨气分解,会造成球团矿的第2次膨胀,产生大量裂纹,分解产生的氢气进入球团矿的内部参与还原。研究结果对了解球团矿氨还原机制,推动氨气在炼铁过程的应用以及低碳技术的发展具有一定的意义。

     

    Abstract: Ammonia, as a hydrogen carrier, has well-established trade routes and relatively low liquefaction costs, and can be directly used as a clean reducing agent for iron ore. Existing studies have provided thermodynamic parameters and reaction activation energy of ammonia reduction through thermodynamic calculations, basic experiments, and kinetic fitting, but the mechanism of ammonia reduction remains unclear. In this study, the reaction behavior, mineral composition and micro-structure of ammonia reduction of pellets at different temperatures and times was investigated, and further combined the changes in reduction expansion rate, thermodynamics analysis, and kinetic analysis, the mechanism of ammonia reduction of pellets were obtained. The results showed that the time for the reduction degree to reach 0.95 decreased from 93.5 min to 43.2 min as the temperature increased from 700 ℃ to 900 ℃. In addition, the mass fraction of nitrogen in the reduced pellet decreased from 0.029% to 0.019%. The results of kinetic fitting indicate that the mechanisms of ammonia reduction of pellets at various temperatures are diverse. The reduction is controlled by diffusion, chemical reaction, and nucleation respectively as the reduction proceeded at 700 ℃. However, the whole reduction duration is controlled by diffusion at 900 ℃. Overall, The reduction between ammonia and hematite mainly occurred on the outside of pellet, and the reduction of hematite to magnetite led to a first swelling of the pellets. The decomposition of ammonia is promoted by the catalysis of metallic iron as the reaction progresses, which led to the second swelling of pellets and the formation of a large number of cracks, and the interior of pellets are further reduced by hydrogen produced from ammonia decomposition. The research results have certain significance for understanding the ammonia reduction mechanism of pellets, promoting the application of ammonia in the iron-making process and the development of low-carbon technologies.

     

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