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氧化亞鐵顆粒氫還原過程的結構演變

Structure evolution in the reduction process of FeO powder by hydrogen

  • 摘要: 采用熱重法實驗研究了773~1273K氧化亞鐵的等溫氫還原動力學,發現873K溫度以上,反應動力學曲線有明顯轉折,說明反應機理發生了變化.在973~1073K的溫度范圍,出現了反常的溫度效應.即反應速率隨溫度升高而減小.為討論產物結構對反應動力學的影響,分別對不同溫度的反應產物,以及一定溫度不同還原狀態(不同反應時間)的產物進行形貌觀察.結果顯示.隨著反應溫度升高,還原產物表面的孔洞增多,枝狀特征顯著增加,而973K和1023K時表面的燒結現象明顯.一定溫度下,隨著反應進行,表面的孔洞增多,并逐漸出現燒結.973K和1023K溫度條件下反應產物大體保留原來的大顆粒外形,而1173K時還原2min開始,就大量出現枝狀產物,并逐漸燒結.結合產物形貌變化和反應動力學曲線,反應前期為界面化學反應控速,隨著反應進行.還原的金屬鐵發生燒結現象,致密的結構阻礙了產物氣體向外擴散,反應控速環節轉變為產物氣體的外擴散,還原速率也隨之降低.

     

    Abstract: The isothermal hydrogen reduction kinetics of FeO powder at 773-1273 K was investigated by thermogravimetry. Above 873 K, there was a turning point in the kinetic curve, which indicated that the reduction mechanism changed. An unusual temperature effect that the reduction rate decreased with increasing temperature was observed from 973 K to 1073 K. To discuss the effect of product structure on the reduction rate of iron oxide, the morphology of samples reduced at different temperatures and for different reaction time was observed by scanning electron microscopy. It was shown that holes on the sample surface increased gradually, the dendritic characteristic appeared with increasing temperature, and the sintered phenomenon was obvious at 973 K and 1023 K. At a certain temperature, holes on the sample surface increased and the sintered phenomenon appeared gradually with prolonging reaction time. At 973 K and 1023 K, the sample kept fairly the original shape, but at 1173 K, just reacted for 2 rain, a large number of dendritic products appeared and sintered gradually. Combining the morphology and kinetic curves, it can be summarized that interfacial chemical reaction is the rate-limiting step in the initial stage of hydrogen reduction. But as the reaction proceeds, the reduced iron sinters and the compact structure of the reduced product hinders the outward diffusion of produced gas. The rate-limiting step changes to the outward diffusion of produced gas, which leads to the decrease of the reduction rate of iron oxide by hydrogen.

     

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