Isothermal reduction kinetics of Panzhihua ilmenite concentrate under 30vol% CO-70vol% N2 atmosphere

The reduction of ilmenite concentrate in 30vol% CO-70vol% N₂ 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 kJ·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 kJ·mol-1. For the whole reduction process, the average activation energy and pre-exponential factor were 98.94-118.33 kJ·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.     

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.     

Investigation of the kinetic mechanism of the demanganization reaction between carbon-saturated liquid iron and CaF_2–CaO–SiO_2-based slags

The demanganization reaction kinetics of carbon-saturated liquid iron with an eight-component slag consisting of CaO–SiO_2–MgO–FeO–MnO–Al_2O_3–TiO_2–CaF_2 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(Mn O), the apparent activation energy of the demanganization reaction was estimated to be 189.46 k J·mol~(–1) in the current study, which indicated that the mass transfer of Mn O 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.     

Hydrometallurgical leaching and kinetic modeling of low-grade manganese ore with banana peel in sulfuric acid

Manganese was leached from a low-grade manganese ore(LGMO) using banana peel as the reductant in a dilute sulfuric acid medium. The effects of banana peel amount, H_2SO_4 concentration, reaction temperature, and time on Mn leaching from the complex LGMO were studied. A leaching efficiency of ～98% was achieved at a leaching time of 2 h, banana peel amount of 4 g, leaching temperature of 120°C,manganese ore amount of 5 g, and sulfuric acid concentration of 15 vol%. The phase, microstructural, and chemical analyses of LGMO samples before and after the leaching process confirmed the successful leaching of manganese. Furthermore, the leaching process followed the shrinking core model and the leaching rate was controlled by a surface chemical reaction(1-(1-x)~(1/3)=kt) mechanism with an apparent activation energy of 40.19 k J·mol~(-1).     

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.     

Kinetics of petroleum coke/biomass blends during co-gasification

The co-gasification behavior and synergistic effect of petroleum coke, biomass, and their blends were studied by thermogravimetric analysis under CO₂ atmosphere at different heating rates. The isoconversional method was used to calculate the activation energy. The results showed that the gasification process occurred in two stages: pyrolysis and char gasification. A synergistic effect was observed in the char gasification stage. This effect was caused by alkali and alkaline earth metals in the biomass ash. Kinetics analysis showed that the activation energy in the pyrolysis stage was less than that in the char gasification stage. In the char gasification stage, the activation energy was 129.1–177.8 kJ/mol for petroleum coke, whereas it was 120.3–150.5 kJ/mol for biomass. We also observed that the activation energy calculated by the Flynn–Wall–Ozawa (FWO) method were larger than those calculated by the Kissinger–Akahira–Sunosen (KAS) method. When the conversion was 1.0, the activation energy was 106.2 kJ/mol when calculated by the KAS method, whereas it was 120.3 kJ/mol when calculated by the FWO method.     

Non-isothermal reduction kinetics of titanomagnetite by hydrogen

Reduction of titanomagnetite (TTM) powders by H2-Ar gas mixtures was investigated under a non-isothermal condition by using a thermogravimetric analysis system. It was found that non-isothermal reduction of TTM proceeded via a dual-reaction mechanism. The first reaction was reduction of TTM to wüstite and ilmenite, whereas the second one was reduction of wüstite and ilmenite to iron and titanium dioxide. By using a new model for the dual reactions, which was in an analytical form and incorporated different variables, such as time, temperature, particle size, and hydrogen partial pressure, rate-controlling steps for the dual reactions were obtained with the apparent activation energies calculated to be 90–98 and 115–132 kJ/mol for the first and second reactions, respectively.     

Comparison of kinetic models for isothermal CO_2 gasification of coal char–biomass char blended char

This study investigated the isothermal gasification reactivity of biomass char(BC) and coal char(CC) blended at mass ratios of 1:3, 1:1, and 3:1 via isothermal thermogravimetric analysis(TGA) at 900, 950, and 1000°C under CO2. With an increase in BC blending ratio, there were an increase in gasification rate and a shortening of gasification time. This could be attributed to the high specific surface area of BC and the high uniformity of carbon structures in CC when compared to those in BC. Three representative gas–solid kinetic models, namely, the volumetric model(VM), grain model(GM), and random pore model(RPM), were applied to describe the reaction behavior of the char. Among them, the RPM model was considered the best model to describe the reactivity of the char gasification reaction. The activation energy of BC and CC isothermal gasification as determined using the RPM model was found to be 126.7 k J/mol and 210.2 k J/mol, respectively. The activation energy was minimum(123.1 k J/mol) for the BC blending ratio of 75%. Synergistic effect manifested at all mass ratios of the blended char, which increased with the gasification temperature.     

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.     

Laboratory Investigation of Zinc Recovery from EAF Dust by Bath Smelting Reduction

Bath smelting reduction for recovering zinc from EAF (Electric Arc Furnace) dust has been investigated in the laboratory. A degree of zinc volatilization of more than 99% was obtained from the process. Temperature has a clear influence on the reduction rate of ZnO in slag. The reduction rate of (ZnO) by [C] is the first order with respect to the content of ZnO in the slag. The apparent activation energy of the (ZnO) reduction reaction is 312 kJ/mol at 1300-1500℃.     

Investigation on preparing boron nitride by nitriding pure boron at 1200–1550 1C

Boron nitride (BN) was prepared by nitriding pure boron (B) deposited on carbon substrates by chemical vapor deposition (CVD). Thermodynamic analysis of preparing BN by nitriding CVD B at 1200–1550 1C was firstly performed. And then, the effects of nitridation conditions, including temperature, nitridation atmosphere and CVD B microstructure, on the conversion of B to BN were analyzed by scanning electron microscopy (SEM), energy dispersion spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Results show that the conversion degree of B to BN firstly increased and then slightly decreased with rising temperature. The nitridation degree was controlled by mutual actions between the nitridation of B and consumption of the effective nitrogen source (NH3). The morphology of products and the reaction mechanism between B and N were influenced by nitridation temperature. At high temperatures (1400–1500 1C), BN with highly ordered microstructure was produced. On using N2–H2 as nitridation atmosphere instead of NH3–H2– N2, no BN was obtained in the studied temperature range. The microstructure and component of BN obtained in nitridation process were little affected by the microstructure of CVD B.     

Extraction and kinetic analysis of Pb and Sr from the leaching residue of zinc oxide ore

NH_4HCO_3 conversion followed by HCl leaching was performed and proven to be effective in extracting Pb and Sr from zinc extracted residual. The mechanism and operating conditions of NH_4HCO_3 conversion, including molar ratio of NH_4HCO_3 to zinc extracted residual,NH_4HCO_3 concentration, conversion temperature, conversion time, and stirring velocity, were discussed, and operating conditions were optimized by the orthogonal test. Experimental results indicate that NH_4HCO_3 conversion at temperatures ranging from 25 to 85°C follows the shrinking unreacted core model and is controlled by inner diffusion through the product layer. The extraction ratios of Pb and Sr under optimized conditions reached 85.15% and 87.08%, respectively. Moreover, the apparent activation energies of Pb and Sr were 13.85 and13.67 k J·mol~(-1), respectively.     

Hot compressive deformation behaviors of Mg–10Gd–3Y–0.5Zr alloy

In this paper, the hot compressive deformation characteristics of a Mg–10Gd–3Y–0.5Zr(GW103K) alloy have been investigated by isothermal compression test at the temperature range of 350–450°C and strain rate range of 0.0001–0.1s~(-1). True stress–strain relationships at various strain rates showed the typical strain hardening and softening stage which is indicative of dynamic recrystallization during deformation. The results showed that the peak stress was obviously dependent on temperature and strain rate. A constitutive equation to describe the deformation process was established based on the hyperbolic sine function. The stress exponent n and apparent activation energy Q were determined to be 3.018 and 203.947 k J/mol, respectively. Microstructure investigation showed that dislocation slipping was the dominant deformation mechanism during the hot deformation at all conditions. However, at the temperatures lower than 400 °C and strain rates higher than 0.01 s~(-1), twinning was observed to be activated, which indicated another deformation mechanism. Dynamic recrystallization and dynamic precipitation were found to occur simultaneously under such deformation condition.     

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.     

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.     

Reduction mechanism of high-chromium vanadium–titanium magnetite pellets by H_2–CO–CO_2 gas mixtures

The reduction of high-chromium vanadium–titanium magnetite as a typical titanomagnetite containing 0.95wt% V2O5 and 0.61wt% Cr2O3 by H2–CO–CO2 gas mixtures was investigated from 1223 to 1373 K. Both the reduction degree and reduction rate increase with increasing temperature and increasing hydrogen content. At a temperature of 1373 K, an H2/CO ratio of 5/2 by volume, and a reduction time of 40 min, the degree of reduction reaches 95%. The phase transformation during reduction is hypothesized to proceed as follows: Fe2O3 → Fe3O4 → FeO → Fe; Fe9 TiO 15 + Fe2Ti3O9 → Fe2.75Ti0.25O4 → FeT iO 3 → TiO 2;(Cr0.15V0.85)2O3 → Fe2VO4; and Cr1.3Fe0.7O3 → FeC r2O4. The reduction is controlled by the mixed internal diffusion and interfacial reaction at the initial stage; however, the interfacial reaction is dominant. As the reduction proceeds, the internal diffusion becomes the controlling step.     

Formation of calcium titanate in the carbothermic reduction of vanadium titanomagnetite concentrate by adding CaCO_3

The formation of calcium titanate in the carbothermic reduction of vanadium titanomagnetite concentrate(VTC) by adding CaCO_3 was investigated. Thermodynamic analysis was employed to show the feasibility of calcium titanate formation by the reaction of ilmenite and Ca CO_3 in a reductive atmosphere, where ilmenite is more easily reduced by CO or carbon in the presence of CaCO_3. The effects of CaCO_3 dosage and reduction temperature on the phase transformation and metallization degree were also investigated in an actual roasting test. Appropriate increase of CaCO_3 dosages and reduction temperatures were found to be conducive to the formation of calcium titanate, and the optimum conditions were a CaCO_3 dosage of 18 wt% and a reduction temperature of 1400°C. Additionally, scanning electron microscopy–energy dispersive spectrometry(SEM–EDS) analysis shows that calcium titanate produced via the carbothermic reduction of VTC by CaCO_3 addition was of higher purity with particle size approximately 50 μm. Hence, the separation of calcium titanate and metallic iron will be the focus in the future study.     

Oxidation behavior of artificial magnetite pellets

The oxidation behavior of artificial magnetite pellets was investigated through measurements of the oxidation degree and mineralogical analysis. The results show that artificial magnetite pellets are much easier to oxidize than natural magnetite. The oxidation is controlled through two different reaction mechanisms. The oxidation of artificial magnetite is dominated by internal diffusion, with an activation energy of 8.40 kJ/mol, at temperatures less than 800℃, whereas it is controlled by chemical reaction, with a reaction activation energy of 67.79 kJ/mol, at temperatures greater than 800℃. In addition, factors such as the oxygen volume fraction and the pellet diameter strongly influence the oxidation of artificial magnetite:a larger oxygen volume fraction and a smaller pellet diameter result in a much faster oxidation process.     

Dynamic recrystallization and precipitation in high manganese austenitic stainless steel during hot compression

Dynamic recrystallization and precipitation in a high manganese austenitic stainless steel were investigated by hot compression tests over temperatures of 950–1150℃ at strain rates of 0.001 s?1-1 s?1. All the flow curves within the studied deformation regimes were typical of dynamic recrystallization. A window was constructed to determine the value of apparent activation energy as a function of strain rate and deformation temperature. The kinetics of dynamic recrystallization was analyzed using the Avrami kinetics equation. A range of apparent activation energy for hot deformation from 303 kJ/mol to 477 kJ/mol is obtained at different deformation regimes. Microscopic characterization confirms that under a certain deformation condition (medium Zener-Hollomon parameter (Z) values), dynamic recrystallization appears at first, but large particles can not inhibit the recrystallization. At low or high Z values, dynamic recrystallization may occur before dynamic precipitation and proceeds faster. In both cases, secondary phase precipitation is observed along prior austenite grain boundaries. Stress relaxation tests at the same deformation temperatures also confirm the possibility of dynamic precipitation. Unexpectedly, the Avrami’s exponent value increases with the increase of Z value. It is associated with the priority of dynamic recrystallization to dynamic precipitation at higher Z values.