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    铜尾矿湿法烟气脱硫脱硝及强化研究

    Wet Flue Gas Desulfurization and Denitrification Using Copper Tailings and Performance Enhancement

    • 摘要: 由于铜尾矿中含有Fe、Mn等过渡金属元素,这些物质在液相中表现出显著的催化氧化性能,同时其富含的Ca、Mg等碱性氧化物组分对SO2和NOx具有良好的吸附特性,这使其作为脱硫脱硝吸收剂具有天然优势。此外,利用铜尾矿处理烟气还兼具原料来源广泛、成本低廉、可同步回收金属离子等优势,符合“以废治废”的环保理念。提出利用铜尾矿浆同时脱除烟气中的SO2和NOx,首先通过基础实验考察其脱硫脱硝性能及相关机理,并探究热活化处理对尾矿活性的强化效果。基础性能与热活化研究结果表明:铜尾矿浆对二氧化硫的脱除效果极为显著,在整个测试周期内均保持100%的去除效率。但该材料对氮氧化物的处理能力相对较弱,即便在优化固液比、反应温度、气体流速及氧含量等关键参数后,其最高脱除率仍仅为45%。针对这一技术瓶颈,本研究采用热活化法对铜尾矿进行改性处理,通过系统实验确定了800 ℃活化温度和120 min活化时间的最佳工艺条件。经此条件活化后,铜尾矿中部分碳酸盐分解生成氧化物,比表面积和活性位点增加,脱硝效率提升至51%,证实热活化对脱硝性能具有明显强化作用。尽管热活化使脱硝效率有所提高,但51%的脱除率仍难以满足实际工程需求。为此,进一步引入氧化剂,旨在通过氧化协同作用大幅提升NOx的去除效果。实验结果表明,在铜尾矿脱硝过程中,高锰酸钾与亚氯酸钠相较于过氧化氢、次氯酸钠等其他氧化剂展现出更为显著的协同效应。其中实验结果表明,当高锰酸钾浓度为38 mmol/L时,系统脱硝效率最高,可达94.5%;而亚氯酸钠在50.6 mmol/L的投加量下,脱硝效果次之,为88.9%。两种氧化剂均能有效将难溶的NO氧化为易吸收的NO2或进一步转化为硝酸盐,从而显著提高脱硝效率。进一步将亚氯酸钠与高锰酸钾复配使用,发现两者具有协同脱硝作用,当氧化剂配比调整为51 mmol/L与25 mmol/L时,系统的脱硝效率达到最优,显著优于单一氧化剂条件下的处理效果。综上所述,铜尾矿经热活化和氧化剂协同强化后,能够在保持高效脱硫的同时,大幅提升脱硝能力,展现出良好的工业应用潜力。

       

      Abstract: Due to the presence of transition metal elements such as Fe and Mn in copper tailings, these substances exhibit significant catalytic oxidation performance in the liquid phase. Meanwhile, the abundant alkaline oxides such as Ca and Mg in it have good adsorption properties for SO2 and NOx, which gives it a natural advantage as a desulfurization and denitrification absorbent. In addition, the utilization of copper tailings for flue gas treatment also has the advantages of wide raw material sources, low cost, and the simultaneous recovery of metal ions, which conforms to the environmental protection concept of "waste treatment with waste". This study proposes the use of copper tailings slurry to simultaneously remove SO2 and NOx from flue gas. Firstly, the desulfurization and denitrification performance and related mechanisms were investigated through basic experiments, and the strengthening effect of thermal activation treatment on the activity of tailings was explored. The results of basic performance and thermal activation studies show that the copper tailings slurry has an extremely significant effect on the removal of sulfur dioxide, maintaining a 100% removal efficiency throughout the test period. However, the material's ability to treat nitrogen oxides is relatively weak. Even after optimizing key parameters such as the solid-liquid ratio, reaction temperature, gas flow rate, and oxygen content, the highest removal rate is still only 45%. To address this technical bottleneck, this study modified the copper tailings by thermal activation. Through systematic experiments, the optimal process conditions of 800°C activation temperature and 120 minutes activation time were determined. After activation under these conditions, some of the carbonates in the copper tailings decomposed into oxides, increasing the specific surface area and active sites, and the denitrification efficiency increased to 51%, confirming that thermal activation has a significant strengthening effect on denitrification performance. Although thermal activation improved the denitrification efficiency, a 51% removal rate is still difficult to meet the actual engineering requirements. Therefore, oxidants were further introduced to significantly enhance the removal effect of NOx through oxidation synergy. Experimental results show that in the denitrification process of copper tailings, potassium permanganate and sodium chlorite exhibit more significant synergistic effects compared to other oxidants such as hydrogen peroxide and sodium hypochlorite. Among them, the experimental results show that when the concentration of potassium permanganate is 38 mmol/L, the system's denitrification efficiency is the highest, reaching 94.5%; while sodium chlorite, at an addition amount of 50.6 mmol/L, has a denitrification efficiency of 83.9%. Both oxidants can effectively oxidize the insoluble NO to the easily absorbable NO2 or further convert it to nitrate, thereby significantly improving the denitrification efficiency. Further, when sodium chlorite and potassium permanganate are used in combination, it was found that they have a synergistic denitrification effect. When the ratio of the oxidants is adjusted to 51 mmol/L and 25 mmol/L, the system's denitrification efficiency reaches the optimum, significantly outperforming the treatment effect under the condition of a single oxidant. In conclusion, after thermal activation and the synergistic enhancement of oxidants, copper tailings can not only maintain high-efficiency desulfurization but also significantly improve denitrification capacity, demonstrating good industrial application potential.

       

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