Isothermal reduction kinetics of Panzhihua ilmenite concentrate under 30vol% CO–70vol% N_2 atmosphere

The reduction of ilmenite concentrate in 30vol% CO–70vol% N_2 atmosphere was characterized by thermogravimetric and differential thermogravimetric(TG–DTG) analysis methods at temperatures from 1073 to 1223 K.The isothermal reduction results show that the reduction process comprised two stages;the corresponding apparent activation energy was obtained by the iso-conversional and model-fitting methods.For the first stage,the effect of temperature on the conversion degree was not obvious,the phase boundary chemical reaction was the controlling step,with an apparent activation energy of 15.55–40.71 k J·mol~(–1).For the second stage,when the temperatures was greater than 1123 K,the reaction rate and the conversion degree increased sharply with increasing temperature,and random nucleation and subsequent growth were the controlling steps,with an apparent activation energy ranging from 182.33 to 195.95 k J·mol~(–1).For the whole reduction process,the average activation energy and pre-exponential factor were 98.94~(–1)18.33 k J·mol~(–1) and 1.820~(–1).816 min~(–1),respectively.     

Isothermal reduction of titanomagnetite concentrates containing coal

The isothermal reduction of the Panzhihua titanomagnetite concentrates (PTC) briquette containing coal under argon atmosphere was investigated by thermogravimetry in an electric resistance furnace within the temperature range of 1250–1350℃. The samples reduced in argon at 1350℃ for different time were examined by X-ray diffraction (XRD) analysis. Model-fitting and model-free methods were used to evaluate the apparent activation energy of the reduction reaction. It is found that the reduction rate is very fast at the early stage, and then, at a later stage, the reduction rate becomes slow and decreases gradually to the end of the reduction. It is also observed that the reduction of PTC by coal depends greatly on the temperature. At high temperatures, the reduction degree reaches high values faster and the final value achieved is higher than at low temperatures. The final phase composition of the reduced PTC-coal briquette consists in iron and ferrous-pseudobrookite (FeTi₂O₅), while Fe_2.75Ti_0.25O₄, Fe_2.5Ti_0.5O₄, Fe_2.25Ti_0.75O₄, ilmenite (FeTiO₃) and wustite (FeO) are intermediate products. The reaction rate is controlled by the phase boundary reaction for reduction degree less than 0.2 with an apparent activation energy of about 68 kJ·mol?1 and by three-dimensional diffusion for reduction degree greater than 0.75 with an apparent activation energy of about 134 kJ·mol?1. For the reduction degree in the range of 0.2–0.75, the reaction rate is under mixed control, and the activation energy increases with the increase of the reduction degree.     

Combustion characteristics of unburned pulverized coal and its reaction kinetics with CO2

The combustion characteristics of two kinds of unburned pulverized coal (UPC) made from bituminous coal and anthracite were investigated by thermogravimetric analysis under air. The reaction kinetics mechanisms between UPC and CO₂ in an isothermal experiment in the temperature range 1000-1100℃ were investigated. The combustion performance of unburned pulverized coal made from bituminous coal (BUPC) was better than that of unburned pulverized coal made from anthracite (AUPC). The combustion characteristic indexes (S) of BUPC and AUPC are 0.47×10-6 and 0.34×10-6%2·min-2·℃-3, respectively, and the combustion reaction apparent activation energies are 91.94 and 102.63 kJ·mol-1, respectively. The reaction mechanism of BUPC with CO₂ is random nucleation and growth, and the apparent activation energy is 96.24 kJ·mol-1. By contrast, the reaction mechanism of AUPC with CO₂ follows the shrinkage spherical function model and the apparent activation energy is 133.55 kJ·mol-1.     

Reduction behavior of hematite in the presence of coke

The reduction kinetics of hematite in the presence of coke as a reductant was studied via isothermal and non-isothermal thermodynamic analyses. The isothermal reduction of hematite was conducted at a pre-determined temperature ranging from 1423 to 1573 K. The results indicated that a higher reduction temperature led to an increased reduction degree and an increased reduction rate. The non-isothermal reduction of hematite was carried out from room temperature to 1573 K at various heating rates from 5 to 15 K·min-1. A greater heating rate gave a greater reduction rate but decreased reduction degree. With an increase in temperature, both the reduction rate and the reduction degree increased at a smaller rate when the temperature was less than 1150 K, and they increased at a higher rate when the temperature was greater than 1150 K before completion of the reduction reaction. Both the isothermal and the non-isothermal reduction behaviors of hematite were described by the Avrami–Erofeev model. For the isothermal reduction, the apparent activation energy and pre-exponential factor were 171.25 kJ·mol-1 and 1.80×105 min-1, respectively. In the case of non-isothermal reduction, however, the apparent activation energy and pre-exponential factor were correlated with the heating rate.     

Phase transformation and reduction kinetics during the hydrogen reduction of ilmenite concentrate

The reduction of ilmenite concentrate by hydrogen gas was investigated in the temperature range of 500 to 1200℃. The microstructure and phase transition of the reduction products were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and optical microscopy (OM). It was found that the weight loss and iron metallization rate increased with the increase of reduction temperature and reaction time. The iron metallization rate could reach 87.5% when the sample was reduced at 1150℃ for 80 min. The final phase constituents mainly consist of Fe, M₃O₅ solid solution phase (M=Mg, Ti, and Fe), and few titanium oxide. Microstructure analysis shows that the surfaces of the reduction products have many holes and cracks and the reactions take place from the exterior of the grain to its interior. The kinetics of reduction indicates that the rate-controlling step is diffusion process control with the activation energy of 89 kJ·mol-1.     

Phase transformation behavior of titanium during carbothermic reduction of titanomagnetite ironsand

The reduction of titanomagnetite (TTM) ironsand, which contains 11.41wt% TiO₂ and 55.63wt% total Fe, by graphite was performed using a thermogravimetric analysis system under an argon gas atmosphere at 1423–1623 K. The behavior and effects of titanium in TTM ironsand during the reduction process were investigated by means of thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. During the reduction procedure, the titanium concentrated in the slag phase, where the phase transformation followed this sequence: FeO + FeTiO₃ → Fe₂TiO₄ → FeTiO₃ → FeTi₂O₅ → TiO₂. The calculated results for the reduction kinetics showed that the carbothermic reduction was controlled by the diffusion of ions through the product layer. Furthermore, the apparent activation energy was 170.35 kJ·mol-1.     

Investigation of the kinetic mechanism of the demanganization reaction between carbon-saturated liquid iron and CaF2-CaO-SiO2-based slags

The demanganization reaction kinetics of carbon-saturated liquid iron with an eight-component slag consisting of CaO-SiO₂-MgO-FeO-MnO-Al₂O₃-TiO₂-CaF₂ was investigated at 1553, 1623, and 1673 K in this study. The rate-controlling step (RCS) for the demanganization reaction with regard to the hot metal pretreatment conditions was studied via kinetics analysis based on the fundamental equation of heterogeneous reaction kinetics. From the temperature dependence of the mass transfer coefficient of a transition-metal oxide (MnO), the apparent activation energy of the demanganization reaction was estimated to be 189.46 kJ·mol-1 in the current study, which indicated that the mass transfer of MnO in the molten slag controlled the overall rate of the demanganization reaction. The calculated apparent activation energy was slightly lower than the values reported in the literature for mass transfer in a slag phase. This difference was attributed to an increase in the "specific reaction interface" (SRI) value, either as a result of turbulence at the reaction interface or a decrease of the absolute amount of slag phase during sampling, and to the addition of calcium fluoride to the slag.     

Kinetic studies on the reduction of iron ore nuggets by devolatilization of lean-grade coal

An isothermal kinetic study of a novel technique for reducing agglomerated iron ore by volatiles released by pyrolysis of lean-grade non-coking coal was carried out at temperature from 1050 to 1200°C for 10–120 min. The reduced samples were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and chemical analysis. A good degree of metallization and reduction was achieved. Gas diffusion through the solid was identified as the reaction-rate-controlling resistance; however, during the initial period, particularly at lower temperatures, resistance to interfacial chemical reaction was also significant, though not dominant. The apparent rate constant was observed to increase marginally with decreasing size of the particles constituting the nuggets. The apparent activation energy of reduction was estimated to be in the range from 49.640 to 51.220 kJ/mol and was not observed to be affected by the particle size. The sulfur and carbon contents in the reduced samples were also determined.     

Sulfuric acid leaching kinetics of South African chromite

The sulfuric acid leaching kinetics of South African chromite was investigated. The negative influence of a solid product layer constituted of a silicon-rich phase and chromium-rich sulfate was eliminated by crushing the chromite and by selecting proper leaching conditions. The dimensionless change in specific surface area and the conversion rate of the chromite were observed to exhibit a proportional relationship. A modified shrinking particle model was developed to account for the change in reactive surface area, and the model was fitted to experimental data. The resulting model was observed to describe experimental findings very well. Kinetics analysis revealed that the leaching process is controlled by a chemical reaction under the employed experimental conditions and the activation energy of the reaction is 48 kJ·mol-1.     

Growth behavior of the magnetite phase in the reduction of hematite via a fluidized bed

To understand the formation and growth mechanism of the magnetite phase during the fluidized reduction of hematite, a high-purity hematite ore was isothermally reduced using a 20vol% CO-80vol% CO₂ gas mixture in a micro-fluidized bed to examine the process of the selective conversion of hematite to magnetite. The micro-structural characteristics of the magnetite phase were investigated using scanning electron microscopy (SEM) and the Brunauer, Emmett, and Teller (BET) method, and the thickness of the magnetite layer was measured and evaluated using statistical analysis. The experimental results showed that the fresh magnetite nuclei were dense needles of different lengths, and the original hematite grains became porous after complete reduction to the magnetite phase. The thickness of the magnetite layer increased with an increase in reduction temperature and reduction time. The growth kinetics of the magnetite layer was investigated, and the value of the activation energy E was estimated to be 28.33 kJ/mol.     

Preparation of Al<Subscript>72</Subscript>Ni<Subscript>8</Subscript>Ti<Subscript>8</Subscript>Zr<Subscript>6</Subscript>Nb<Subscript>3</Subscript>Y<Subscript>3</Subscript> amorphous powders and bulk materials

Amorphous Al₇₂Ni₈Ti₈Zr₆Nb₃Y₃ powders were successfully fabricated by mechanical alloying. The microstructure, glass-forming ability, and crystallization behavior of amorphous Al₇₂Ni₈Ti₈Zr₆Nb₃Y₃ powders were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The isothermal crystallization kinetics was analyzed by the Johnson–Mehl–Avrami equation. In the results, the supercooled liquid region of the amorphous alloy is as high as 81 K, as determined by non-isothermal DSC curves. The activation energy for crystallization is as high as 312.6 kJ·mol?1 obtained by Kissinger and Ozawa analyses. The values of Avrami exponent (n) imply that the crystallization is dominated by interface-controlled three-dimensional growth in the early stage and the end stage and by diffusion-controlled two- or three-dimensional growth in the middle stage. In addition, the amorphous Al₇₂Ni₈Ti₈Zr₆Nb₃Y₃ powders were sintered under 2 GPa at temperatures of 673 K and 723 K. The results show that the Vickers hardness of the compacted powders is as high as Hv 1215.     

Effect of CO<Subscript>2</Subscript> and H<Subscript>2</Subscript>O on gasification dissolution and deep reaction of coke

To more comprehensively analyze the effect of CO₂ and H₂O on the gasification dissolution reaction and deep reaction of coke, the reactions of coke with CO₂ and H₂O using high temperature gas-solid reaction apparatus over the range of 950-1250℃ were studied, and the thermodynamic and kinetic analyses were also performed. The results show that the average reaction rate of coke with H₂O is about 1.3-6.5 times that with CO₂ in the experimental temperature range. At the same temperature, the endothermic effect of coke with H₂O is less than that with CO₂. As the pressure increases, the gasification dissolution reaction of coke shifts to the high-temperature zone. The use of hydrogen-rich fuels is conducive to decreasing the energy consumed inside the blast furnace, and a corresponding high-pressure operation will help to suppress the gasification dissolution reaction of coke and reduce its deterioration. The interfacial chemical reaction is the main rate-limiting step over the experimental temperature range. The activation energies of the reaction of coke with CO₂ and H₂O are 169.23 kJ·mol-1 and 87.13 kJ·mol-1, respectively. Additionally, water vapor is more likely to diffuse into the coke interior at a lower temperature and thus aggravates the deterioration of coke in the middle upper part of blast furnace.     

Effect of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> on the crystallization behavior of glass-ceramics produced from naturally cooled yellow phosphorus furnace slag

CaO-Al₂O₃-SiO₂ (CAS) glass-ceramics were prepared via a melting method using naturally cooled yellow phosphorus furnace slag as the main raw material. The effects of the addition of Fe₂O₃ on the crystallization behavior and properties of the prepared glass-ceramics were studied by differential thermal analysis, X-ray diffraction, and scanning electron microscopy. The crystallization activation energy was calculated using the modified Johnson-Mehl-Avrami equation. The results show that the intrinsic nucleating agent in the yellow phosphorus furnace slag could effectively promote the crystallization of CAS. The crystallization activation energy first increased and then decreased with increasing amount of added Fe₂O₃. At 4wt% of added Fe₂O₃, the crystallization activation energy reached a maximum of 676.374 kJ·mol-1. The type of the main crystalline phase did not change with the amount of added Fe₂O₃. The primary and secondary crystalline phases were identified as wollastonite (CaSiO₃) and hedenbergite (CaFe(Si₂O₆)), respectively.     

LiNiPO4前驱体固相反应合成动力学及电容性能

以氢氧化锂、磷酸二氢铵和醋酸镍为原料,以聚乙二醇PEG-400为表面活性剂,采用前驱体固相活化法制备LiNiPO4纳米晶材料.固相制备过程的活化能E=81.08 kJ·mol-1,过程动力学为二维相界面扩散反应机理.前驱体生成LiNiPO4的反应符合界面反应指数成核机理,活化能E1=11.82 kJ·mol-1,指前因子lnA=13.82;LiNiPO4晶体生长过程具有较小的活化能E2=17.73 kJ·mol-1;Li3PO4转化反应和反应体系物系晶化过程符合二维相界面扩散反应机理,其是制备过程可控制的重要步骤.材料复合电极LiNiPO4+Nafion/C在0.5 mol·L-1H2SO4中具有典型的电容性能,电极比电容为214 F·g-1,经1 000次循环,电极电容量不但没有衰减反而略有增加,是潜在的电容器材料.     

Kinetic study on the direct nitridation of silicon powders diluted with α-Si3N4 at normal pressure

Silicon nitride (Si₃N₄) powders were prepared by the direct nitridation of silicon powders diluted with α-Si₃N₄ at normal pressure. Silicon powders of 2.2 μm in average diameter were used as the raw materials. The nitriding temperature was from 1623 to 1823 K, and the reaction time ranged from 0 to 20 min. The phase compositions and morphologies of the products were analyzed by X-ray diffraction and scanning electron microscopy, respectively. The effects of nitriding temperature and reaction time on the conversion rate of silicon were determined. Based on the shrinking core model as well as the relationship between the conversion rate of silicon and the reaction time at different temperatures, a simple model was derived to describe the reaction between silicon and nitrogen. The model revealed an asymptotic exponential trend of the silicon conversion rate with time. Three kinetic parameters of silicon nitridation at atmospheric pressure were calculated, including the pre-exponential factor (2.27 cm·s^?1) in the Arrhenius equation, activation energy (114 kJ·mol^?1), and effective diffusion coefficient (6.2×10^?8 cm²·s^?1). A formula was also derived to calculate the reaction rate constant.     

Synthesis of glass ceramics from kaolin and dolomite mixture

Cordierite-and anorthite-based binary glass ceramics of the CaO-MgO-Al₂O₃-SiO₂ (CMAS) system were synthesized by mixing local and abundant raw minerals (kaolin and doloma by mass ratio of 82/18). A kinetics study reveals that the activation energy of crystallization (Ea) calculated by the methods of Kissinger and Marotta are 438 kJ·mol-1 and 459 kJ·mol-1, respectively. The Avrami parameter (n) is estimated to be approximately equal to 1, corresponding to the surface crystallization mechanism. X-ray diffraction (XRD) analysis shows that the anorthite and cordierite crystals are precipitated from the parent glass as major phases. Anorthite crystals first form at 850℃, whereas the μ-cordierite phase appears after heat treatment at 950℃. Thereafter, the cordierite allotropically transforms to α-cordierite at 1000℃. Complete densification is achieved at 950℃; however, the density slightly decreases at higher temperatures, reaching a stable value of 2.63 kg·m-3 between 1000℃ and 1100℃. The highest Vickers hardness of 6 GPa is also obtained at 950℃. However, a substantial decrease in hardness is recorded at 1000℃; at higher sintering temperatures, it slightly increases with increasing temperature as the α-cordierite crystallizes.     

Effects of aging treatment on the microstructure and superelasticity of columnar-grained Cu<Subscript>71</Subscript>Al<Subscript>18</Subscript>Mn<Subscript>11</Subscript> shape memory alloy

The effect of aging treatment on the superelasticity and martensitic transformation critical stress in columnar-grained Cu₇₁Al₁₈Mn₁₁ shape memory alloy (SMA) at the temperature ranging from 250°C to 400°C was investigated. The microstructure evolution during the aging treatment was characterized by optical microscopy, scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The results show that the plate-like bainite precipitates distribute homogeneously within austenitic grains and at grain boundaries. The volume fraction of bainite increases with the increase in aging temperature and aging time, which substantially improves the martensitic transformation critical stress of the alloy, whereas the bainite only slightly affects the superelasticity. This behavior is attributed to a coherent relationship between the bainite and the austenite, as well as to the bainite and the martensite exhibiting the same crystal structure. The variations of the martensitic transformation critical stress and the superelasticity of columnar-grained Cu₇₁Al₁₈Mn₁₁ SMA with aging temperature and aging time are described by the Austin–Rickett equation, where the activation energy of bainite precipitation is 77.2 kJ·mol?1. Finally, a columnar-grained Cu₇₁Al₁₈Mn₁₁ SMA with both excellent superelasticity (5%–9%) and high martensitic transformation critical stress (443–677 MPa) is obtained through the application of the appropriate aging treatments.