离子型稀土矿山淋洗及尾水富集试验研究

对浸矿后离子型稀土原地浸矿场采用清水进行淋洗，在184天的清水淋洗过程中，尾水氨氮值从最开始的507mg/L，降低至140mg/L，淋洗尾水pH4.52~3.10。淋洗尾水采用两级反渗透膜分离，既回收有价资源稀土，又能使出水氨氮达标。结果表明，产水氨氮浓度稳定低于15mg/L，对稀土的截留率高于98.25%，浓水中稀土离子平均浓度313.4mg/L，可进一步回收稀土资源。     

地应力条件下的凿岩爆破数值模拟

为了研究地应力对凿岩爆破的影响,采用DDA方法模拟爆炸应力波作用下考虑地应力条件时的单孔和多孔凿岩爆破破岩过程。模拟发现,随着初始地应力水平的增加,裂纹扩展半径和破岩区域面积减小,裂纹发育主方向趋于地应力的最大主应力方向,初始地应力对裂纹的抑制和引导作用明显;初始地应力水平的增加,对拉伸裂纹的抑制作用更为显著,从而降低了拉伸破坏对爆破破岩的贡献。模拟也表明,在初始地应力存在的条件下,通过对爆破载荷和炮孔布置进行针对性的优化,可以克服地应力带来的影响,并取得预期的爆破效果。本研究对地应力条件下的凿岩爆破工程具有理论和参考意义。     

Effect of scandium and zirconium alloying on microstructure and gaseous hydrogen storage properties of YFe3

RM₃ compounds (R = rare earth metals, M = transition metals) have rarely been studied for gaseous hydrogen storage applications because of unfavorable thermodynamics. In this work, the hydrogen storage properties of a single-phase YFe₃ alloy were improved by non-stoichiometric composition and alloying with Sc and Zr. Only the Y_1.1–ySc_yFe₃ (y = 0.22, 0.33) alloys consist of a single rhombohedral phase. The Sc substitution for Y leads to the reduction in the unit cell volume of the YFe₃ phase, and thus significantly increases the dehydriding equilibrium pressure and decreases the dehydrogenation temperature. The alloy Y_0.77Sc_0.33Fe₃ delivers a decomposition enthalpy change of 33.54 kJ/mol and a lowest dehydrogenation temperature of 135 °C, in comparison with 38.99 kJ/mol and 165 °C for the alloy Y_1.1Fe₃. The Zr substitution causes a similar thermodynamic destabilization effect, but the composition and microstructure of Y–Zr–Fe alloys need to be further optimized.     

Effect of Pr-Ga dual-alloys diffusion on magnetic properties and thermal stability of hot-deformed PrNd-Fe-B magnets

To investigate the influence of the addition of Pr–Ga alloys on magnetic properties and morphology of materials, the hot-deformed PrNd-Fe-B magnets were prepared by the addition of Pr–Ga alloys using a dual-alloys diffusion. The room-temperature coercivity of the hot-deformed PrNd-Fe-B magnets increases substantially from 1.68 to 2.34 T, while the remanence decreases from 1.42 to 1.24 T, by the addition of 5 wt% Pr–Ga alloys. Moreover, the thermal stability of coercivity improves from ?0.46%/^oC to ?0.42%/^oC. Two types of grain boundary phases (PrNd-rich and PrNd-Ga-rich) are generated at grain boundaries by microstructural analysis, resulting in the decrease of Fe element concentration from more than 60% to about 10% at grain boundaries. The decrease of ferromagnetic element concentration at grain boundaries and the refinement of grain are considered to be the main reasons for the improvement of coercivity and thermal stability.     

Observation of table-like magnetocaloric effect and large refrigerant capacity in Nd6Fe13Pd1–xCux compounds

The table-like magnetocaloric effect is significant for the magnetic refrigeration applications above 20 K based on the Ericsson cycle. Herein, we prepared a series of Nd₆Fe₁₃Pd_1–xCu_x (x = 0.05, 0.1, 0.15) compounds by the arc-melting method. These compounds show the single crystalline phase in the tetragonal Nd₆Fe₁₃Si-type structure with the space group I4/mcm. A magnetic phase transition from ferromagnetism to antiferromagnetism and a metamagnetic transition from the antiferromagnetic state to the ferromagnetic state are observed in each of the compounds. The compounds exhibit table-like magnetocaloric effects with large refrigerant capacities. A constant ΔS_M in a temperature span of 40 K in the Nd₆Fe₁₃Pd_0.85Cu_0.15 compound are observed. For a field change of 0–5 T, the peak values of –ΔS_M for the Nd₆Fe₁₃Pd_0.95Cu_0.05, Nd₆Fe₁₃Pd_0.90Cu_0.10, and Nd₆Fe₁₃Pd_0.85Cu_0.15 compounds are estimated to be 4.8, 4.6 and 4.4 J/(kg·K) with corresponding refrigerant capacity values of 323, 331 and 316 J/kg, respectively. The obtained table-like magnetocaloric effects with large refrigerant capacities as well as fairly small thermal and magnetic hysteresis deem these series of compounds good candidates for single-phase magnetic refrigeration based on the Ericsson cycle.     

Behavior of phase transformation of Baotou mixed rare earth concentrate during oxidation roasting

Based on the new process named “Combination Method” for metallurgy and separation of Baotou mixed rare earth concentrate (BMREC), the aim of this paper is to clearly elucidate the phase change behavior of BMREC without additives during oxidative roasting at 450–800 °C. The results indicate that the bastnaesite in BMREC is decomposed at 450–550 °C, the weight loss is about 10.3 wt%, and the activation energy (E) is 144 kJ/mol. The bastnaesite in BMREC is decomposed into rare earth fluoride, rare earth oxides (La₂O₃, Ce₇O₁₂, Pr₆O₁₁ and Nd₂O₃), and CO₂, particularly, with the increase of roasting temperature, bastnaesite in BMREC is more completely decomposed into LaF₃, which causes a decrease in leaching rate of La during the HCl leaching process. Additionally, the maximum cerium oxidation efficiency reaches about 60 wt% when the roasting temperature is equal to or above 500 °C, and the oxidation reaction rate of cerium increases with the increasing roasting temperature.     

Revealing active species of CePO4 catalyst for selective catalytic reduction of NOx with NH3

Revealing the active species of the catalyst is conducive to the design of more efficient catalyst. Herein, we tried to demonstrate the roles of amorphous and crystalline structures on CePO₄ catalyst during selective catalytic reduction (SCR) of NO_x by NH₃. Higher calcination temperature promotes the transfer of amorphous structure to crystalline structure on the surface of CePO₄. Both amorphous and crystalline CePO₄ species on CePO-X samples can provide acid sites for NH₃ adsorption, but the former can provide more acid sites. The superior redox property of surface amorphous CePO₄ species contributes to its high NH₃-SCR activity at low temperature, but it also leads to the decrease of high temperature (>350 °C) NH₃-SCR activity due to the oxidation of NH₃. In contrast, crystalline CePO₄ species shows high activity only at high temperature because of its poor redox property. Therefore, it can be inferred that amorphous and crystalline structures on CePO₄ catalyst can be the efficient active species of NH₃-SCR at low and high temperature, respectively.     

In-situ measurement of mineral phase transition and kinetics in roasting process of Bayan Obo mixed rare earth concentrate by sodium carbonate

In this study, the Bayan Obo rare earth concentrates mixed with Na₂CO₃ were used for roasting research. The phase change process of each firing stage was analyzed. The kinetic mechanism model of the continuous heating process was calculated. This study aims to recover valuable elements and optimize the production process to provide a certain theoretical basis. Using X-ray diffraction (XRD), Fourier infrared spectroscopy, scanning electron microscopy with energy dispersive spectrometry, the reaction process and the existence of mineral phases were analyzed. The variable temperature XRD and thermogravimetric method were used to calculate the roasting kinetics. The phase transition results show that carbonate-like substances first decompose into fine mineral particles, and CaO, MgO, and SiO₂ react to form silicates, causing hardening. Further, REPO₄ and NaF can directly generate CeF₃ and CeF₄ at high temperatures, and a part of CeF₄ and NaF forms a solid solution substance Na₃CeF₇. Rare earth oxides calcined at a high temperature of 750 °C were separated to produce Ce_0.6Nd_0.4O_1.8, Ce₄O₇, and LaPrO_3+x. Then, BaSO₄, Na₂CO₃, and Fe₂O₃ react to form barium ferrite BaFe₁₂O₁₉; the kinetic calculation results show that during the continuous heating process, the apparent activation energy E reaches the minimum in the entire reaction stage in the temperature range of 440–524 °C, and the reaction order n reaches the maximum, which indicates that the decomposition product REFO significantly impacts the reaction system and reduces the activation energy. The mechanism function is F(α) = [?ln (1?α)]^1/3. The reaction order n reaches the minimum in the temperature range of 680–757 °C, and the apparent activation energy E is large. The difficulty of the reaction increases during the final stage. The reaction mechanism function is F(α) = [1?(1?α)^1/3]². Observing the entire reaction stage, the step of controlling the reaction rate changes from random nucleation to three-dimensional diffusion (spherical symmetry).