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冶金含鐵塵泥制備的Mn–Ce摻雜Fe基催化劑及特性

Preparation and characteristics of Mn–Ce-doped Fe-based catalysts using metallurgical dust and mud containing iron

  • 摘要: 針對冶金工業固廢–含鐵冶金塵泥組分復雜的特性,結合當前冶金燒結過程NOx排放也是鋼鐵行業污染治理的重中之重的現狀,提出對冶金含鐵塵泥進行改性制備摻雜低溫催化劑的思路,并制備了Mn–Ce摻雜的含鐵塵泥基催化劑(Mn0.05Ce0.1/ADM,ADM分別代表acidolysis,dust 和mud),研究結果表明在170~430 ℃寬溫度區間內,Mn0.05Ce0.1/ADM催化劑NOx脫除率達到90%以上,并表現出優異的SO2和H2O抗性,抗水抗硫性測試表明Mn0.05Ce0.1/ADM催化劑得益于Fe、Ce優異的抗水抗硫性,其活性組分具有較好的分散性和優異的介孔結構,并降低了表面結晶度. Mn摻雜使催化劑在犧牲一定Ce3+濃度和高價態Mnx+離子的同時提高了Fe3+的濃度,結果使其具有最均衡脫硝活性. 此外,Fe–Ce–Mn間的協同作用改善了催化劑的表面酸性從而增加了Lewis酸性位點,進而促進靜電極化激活NO2和硝酸鹽物種生成. 研究結果可為冶金固廢的高附加值利用及以廢治污的思路提供一定理論參考.

     

    Abstract: Metallurgical solid wastes, such as metallurgical dust and mud containing iron, are formed during metallurgical sintering. They are composed of complex components and are harmful to the environment. Alongwith the current metallurgical sintering process, NOx emission control is the top priority of pollution control in the steel industry. This paper proposes a new idea of preparing doped low-temperature catalysts using metallurgical dust and mud containing iron. Herein, the metallurgical iron-containing mud was modified by acid leaching, and the products were doped with Ce and Mn by the precipitation method to prepare a new type of catalyst. The prepared Mn–Ce-doped mud-based catalyst (Mn0.05Ce0.1/ADM, the ADM represents the dust and mud from acidolysis) was characterized via X-ray diffraction, nitrogen adsorption/desorption isotherm method, scanning electron microscopy, X-ray photoelectron spectroscopy, temperature-programmed desorption of ammonia, and temperature-programmed reduction of hydrogen. The results showed that Mn0.05Ce0.1/ADM achieveda NOx removal rate of >90% within a wide temperature range from 170 ℃ to 430 ℃. Moreover, itshowed excellent SO2 and H2O resistance. A microstructural analysis revealed that the strong interaction between Fe–Ce–Mn could improve the surface acidity of the catalyst, thus increasing Lewis acid sites. Further, the active components of Mn0.05Ce0.1/ADM prepared by Ce and Mn exhibited good dispersion and an excellent mesoporous structure. In particular, Mn doping could inhibit the crystallization degree on the catalyst surface, improve the dispersed state of the active components in Mn0.05Ce0.1/ADM, and help improve the catalyst SCR (Selective Catalytic Reduction) activity. Combined with theanalysis of the factors influencing the catalyst, the results showed that the Ce–Mn doped catalyst increased the Fe3+ concentration while sacrificing a certain amount of Ce3+ and high-valent Mn+, achieving the most balanced denitration activity. Mn0.05Ce0.1/ADM formed more NO active centers by increasing the Lewis acid content to promote the generation of nitrate species and NO2. Moreover, Mn doping enhanced the Fe–Ce synergy, which makes active species (Mn–Ce–Fe) easier reduction. In particular, the increase in surface oxygen mobility could significantly improve the low-temperature activity of the catalyst. The water and sulfur resistance tests of the three catalysts (Ce0.1/ADM、Mn0.05/ADM、Mn0.05Ce0.1/ADM) showed that Mn0.05Ce0.1/ADM benefited from the excellent water and sulfur resistance of Fe and Ce. The results showed that doping Ce into ADM inhibited the adsorption of H2O molecules on the active component β-MnO2 and also the reaction of SO2 molecules with the component. The results reported herein can provide theoretical references for the high-value-added utilization of metallurgical solid wastes.

     

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