In gaseous reduction of iron ore fines,alkaline earth oxides have profound effects on the precipitation behavior of fresh metallic iron on the particle surface.In this work,in situ observation was performed to reveal the influence of alkaline earth oxides on the precipitation morphology and micro-structure variation of fresh metallic iron from microscopic level by simulation of the gas-solid reaction condition on the surface of ore particles.Experimental results indicate that doping MgO in the particle surface can inhibit the reduction of iron oxide and however doping CaO,SrO and BaO promote;all alkaline earth oxides tested in this study can change the precipitation morphology of fresh metallic iron;minimum doping mole fraction of one oxide to inhibit iron whiskers growth(NAO) is related to its cation radius(r A2+) and its extranuclear electronic layers(nA2+),which can be expressed as NAO=1.3×10-5 r2 A2+(~nA^(2+))^(1/2)
To process optimization and improve the degree of reduction, a two-step experiment was designed. The experiment was carried out in the micro-fluidized bed. The reactor in the micro-fluidized bed is operated as a differential reactor to ensure an equal temperature and residence time with the reactor volume. The experiment used Brazilian iron ore and reducing gas of CO. The operating temperature was 400 to 800 ℃ and the residence time was between 10 and 60 min. In correspondence with experiment, microscopic technique was applied too. The test shows that temperature and residence time of the pre-reduction stage have an important effect on the degree of reduction. By using two-step experiment, the maximum value of reduction degree increases by 44.1% compared with the maximum value of traditional reduction experiment. Microscopic analysis shows that the specific surface area, surface morphology and texture of reduced iron ore after pre-reduction stage have an important effect on the degree of final reduction too.
Micro-fluidized bed reactor is a new research method for the reduction of iron ore fines.The reactor is operated as a differential reactor to ensure a constant gas concentration and temperature within the reactor volume.In order to understand the dynamic process of the reduction reaction in micro-fluidized bed,a series of kinetic experiments were designed.In the micro-fluidized bed,the use of shrinking core model describes the dynamic behavior of reduction of iron ore.And the apparent activation energy is calculated in the range of 700-850 ℃ while the initial atmosphere is 100% content of CO.
LIN Yin-heGUO Zhan-chengTANG Hui-qingREN ShanLI Jing-wei
Growth process of iron whiskers and mechanism of CaO influence on precipitation morphology of metallic iron at the gas-solid interfaces was studied. Analytical reagents of Fe(NO3)3 and Ca(NO3)2 aqueous solution were used to prepare sheet film sample of Fe2O3-CaO by thermal decomposition at high temperature. In-situ observation was conducted using a stereo optical microscope and a hot-stage. And reduction kinetics of samples was studied by thermo gravimetric (TG) method. Some samples after reduction were analyzed by using the scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and fourier transform infrared (FT-IR) spectrometer. Results indicate that during the reduction of iron oxides with CO, metallic iron is mostly precipitated as whisker and the precipitation behavior mainly depends on reduction rate. Doping CaO can significantly increase the reduction rate and effectively change the precipitation morphology of metallic iron after the reduction. When CaO doping concentration is less than 4% (mass percent), CaO can promote whisker formation of reduced iron; as it reaches 6% (mass percent), CaO inhibits iron whiskers growth; as it is more than 8% (mass percent), no whiskers could be observed. Therefore, controlling the quantity of Ca2+ is effective to control the formation and growth of iron whiskers during gaseous reduction and thus eliminating ore grain sticking caused by intertexture of iron whiskers.
