This paper reports the recoveries of iron, chromium, and nickel from pickling sludge using coal-based smelting reduction. The influences of slag basicity (CaO/SiO₂, which is controlled by high phosphorus oolitic hematite iron ores), reduction temperature, reduction time, and the C/O mole ratio on the recoveries of Fe, Cr, and Ni are investigated systematically. The experimental results show that high recoveries of Fe (98.91%), Cr (98.46%), and Ni (99.44%) are produced from pickling sludge with optimized parameters for the smelting reduction process. The optimized parameters are a slag basicity of 1.5; a reduction temperature of 1550 °C, a reduction time of 90 min, and a C/O mole ratio of 2.0. These parameters can be used as technical support for the recycling of pickling sludge with pyrometallurgy.

A novel smelting reduction process called pre-reduction in rotary kiln and total oxygen melting pool is a promising route to reduce environmental pollution from the ironmaking industry. In this paper, the process parameters and appropriate efficiency of reduction in the pre-reduction process of the rotary kiln were investigated via the detection of the metallization rate, phase composition, and internal morphology of the product combining with the analysis of the off-gas. The results indicated that the parameters of reduction temperature, reduction holding time, and coal ratio have a remarkable influence on the metallization rate. The reduction temperature has the most significant effect, followed by the reduction time and the coal ratio. Furthermore, under the condition of reduction temperature 1000 °C, holding time 30 min, coal ratio = 1, a product with a metallization rate of more than 70% can be obtained, which meets the requirements of the rotary kiln process, and its CO₂/CO value of the pre-reduction endpoint is appropriate. Continue to increase the temperature, holding time, and coal ratio can raise the metallization rate of the pellets, but only a little improvement and may cause reoxidation of the product.

The partition behavior of alloying elements between the γ’ and γ phases in Nickel-based alloys was investigated by using infinite dilution activity coefficient and activity interaction parameter. The results showed that the preferential partition behavior of elements in the γ’ and γ phases is related to its infinite dilution activity coefficient ( ln γ i 0 \ln \gamma _i^0 ). When ln γ i 0 ≪ 0 \ln \gamma _i^0 \ll 0 , the element i has a strong tendency to partition in the γ’ phase; When ln γ i 0 \ln \gamma _i^0 approaches to zero, the element i has preferentially partition to the matrix γ phase. In addition, the partition behavior of element i in the γ’ and γ phases is also affected by the third element j in Nickel-based alloys, and this effect can be distinguished by the sign of the second-order activity interaction parameter ρ i i j \rho _i^{ij} .

The reduction process inside the ore pre-reduction rotary kiln involves a series of physicochemical reactions, and in-depth understanding of the reduction behavior is helpful to improve the product quality and productivity. This paper reports a three-dimensional steady state mathematical model based on computational fluid dynamics, which considers heat transfer, mass transfer and chemical reactions inside the rotary kiln. A user-defined functions (UDFs) program in C language is developed to define physical parameters and chemical reactions, and calculate the heat and mass transfer between freeboard and bed regions. The model is validated by measurement data and is then used to investigate the detailed information inside the rotary kiln. The results show that there is a temperature gradient in the bed, which is maximal near the kiln tail and decreases gradually as the reduction process progresses. The result also confirms that the reduction of FeO to Fe is the limiting step of the whole reduction process because this reaction requires a higher reduction potential. Furthermore, the influence of C/O mole ratio and fill degree are analyzed by comparing the average bed temperature, reduction potential and metallization ratio.

With an attempt to improve the thermoelectric properties of type I clathrates in the Ba-Ga-Si system, we introduce Cu into the framework of the crystal structure. Single crystals are prepared in Ga-flux and characterized by X-ray diffraction techniques and transport measurements for the structural and thermoelectric properties. Our composition analyses show that only a small amount of Cu is determined in the clathrates. The single crystal X-ray diffraction data refinements confirm that Ga atoms prefer the 6c and 24k sites and avoid the 16i sites in the crystal structure. The small amount of Cu affects the crystal structure by compressing the tetrakaidecahedral cage along the direction perpendicular to the six-atom-ring plane. This could be the reason for the high charge carrier concentration, and low electrical resistivity and Seebeck coefficient. We analyze the principal mechanism for our observation and conclude that the Cu substitution can adjust some subtle details of the structure, maintaining the Zintl rule in the type I clathrates.