冶金含铁尘泥制备的Mn–Ce掺杂Fe基催化剂及特性

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

  • 摘要: 针对冶金工业固废–含铁冶金尘泥组分复杂的特性,结合当前冶金烧结过程NOx排放也是钢铁行业污染治理的重中之重的现状,提出对冶金含铁尘泥进行改性制备掺杂低温催化剂的思路,并制备了Mn–Ce掺杂的含铁尘泥基催化剂(Mn0.05Ce0.1/ADM,ADM分别代表acidolysis,dust 和mud),研究结果表明在170~430 ℃宽温度区间内,Mn0.05Ce0.1/ADM催化剂NOx脱除率达到90%以上,并表现出优异的SO2和H2O抗性,抗水抗硫性测试表明Mn0.05Ce0.1/ADM催化剂得益于Fe、Ce优异的抗水抗硫性,其活性组分具有较好的分散性和优异的介孔结构,并降低了表面结晶度. Mn掺杂使催化剂在牺牲一定Ce3+浓度和高价态Mnx+离子的同时提高了Fe3+的浓度,结果使其具有最均衡脱硝活性. 此外,Fe–Ce–Mn间的协同作用改善了催化剂的表面酸性从而增加了Lewis酸性位点,进而促进静电极化激活NO2和硝酸盐物种生成. 研究结果可为冶金固废的高附加值利用及以废治污的思路提供一定理论参考.

     

    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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