Fluidized magnetization roasting of refractory siderite-containing iron ore via preoxidation-low-temperature reduction

Magnetization roasting is one of the most effective way of utilizing low-grade refractory iron ore.However,the reduction roasting of siderite(FeCO3)generates weakly magnetic wüstite,thus reducing iron recovery via weak magnetic separation.We systematically studied and proposed the fluidized preoxidation-low-temperature reduction magnetization roasting process for siderite.We found that the maghemite generated during the air oxidation roasting of siderite would be further reduced into wüstite at 500 and 550℃due to the unstable intermediate product magnetite(Fe_(3)O_(4)).Stable magnetite can be obtained through maghemite reduction only at low temperature.The optimal fluidized magnetization roasting parameters included preoxidation at 610℃for 2.5 min,followed by reduction at 450℃for 5 min.For roasted ore,weak magnetic separation yielded an iron ore concentrate grade of 62.0wt%and an iron recovery rate of 88.36%.Compared with that of conventional direct reduction magnetization roasting,the iron recovery rate of weak magnetic separation had greatly improved by 34.33%.The proposed fluidized preoxidation-low-temperature reduction magnetization roasting process can realize the efficient magnetization roasting utilization of low-grade refractory siderite-containing iron ore without wüstite generation and is unlimited by the proportion of siderite and hematite in iron ore.

Preparation of ZrB_(2)-ZrO_(2)-SiC Composite Powder by Carbothermal Reduction from Zircon

Using zircon,boric acid and carbon black as starting materials,ZrB_(2)-ZrO_(2)-SiC composite powder was synthesized by calcining at 1500℃in flowing argon atmosphere.The effects of the soaking time(3,6 and 9 h)and the addition of additive AlF_(3)(0,0.5%,1.0%,1.5%,2.0%and 2.5%,by mass)on the phase composition and the microstructure of the synthesized products were investigated.The results show that:(1)ZrB_(2)-ZrO_(2)-SiC composite powder can be synthesized by carbothermal reduction at 1500℃in flowing argon atmosphere;ZrB_(2) and ZrO_(2) are granular-like,and SiC crystals are fiberous;(2)with the soaking time increasing,the amount of ZrB_(2) increases,the amounts of m-ZrO_(2) and SiC decrease,and the total amount of non-oxides ZrB_(2),SiC and ZrC gradually increases;the optimal soaking time is 3 h;(3)compared with the sample without AlF_(3),the sample with 0.5% AlF_(3) has decreased m-ZrO_(2)amount,noticeably increased ZrB_(2) amount but decreased SiC amount;however,when the addition of AlF_(3) increases from 0.5%to 2.5%,the m-ZrO_(2) amount increases,the ZrB_(2)amount decreases,and the SiC amount changes slightly;the optimum AlF_(3)addition is 0.5%.

Investigation of β-Ga_(2)O_(3) thick films grown on c-plane sapphire via carbothermal reduction

We investigated the influence of the growth temperature, O_(2) flow, molar ratio between Ga_(2)O_(3) powder and graphite powder on the structure and morphology of the films grown on the c-plane sapphire(0001) substrates by a carbothermal reduction method. Experimental results for the heteroepitaxial growth of β-Ga_(2)O_(3) illustrate that β-Ga_(2)O_(3) growth by the carbothermal reduction method can be controlled. The optimal result was obtained at a growth temperature of 1050 °C. The fastest growth rate of β-Ga_(2)O_(3) films was produced when the O_(2) flow was 20 sccm. To guarantee that β-Ga_(2)O_(3) films with both high-quality crystal and morphology properties, the ideal molar ratio between graphite powder and Ga_(2)O_(3) powder should be set at 10 : 1.

Preparation of TiC powders by carbothermal reduction method in vacuum

The preparation of fine TiC powders by carbothermal reduction of TiO2 in vacuum was investigated by XRD,SEM,XRF and laser particle sizer.Thermodynamic analysis indicates that it is easy to prepare TiC in vacuum and the formation sequence of products are Ti4O7（Magneli phase）,Ti3O5,Ti2O3,TiCxO1-x and TiC with the increase of reaction temperature.Experimental results demonstrate that TiC powders with single phase are obtained with molar ratio of TiO2 to C ranging from 1：3.2 to 1：6 at 1 550 ℃ for 4 h when the system pressure is 50 Pa,and TiC1.0 is gained when the molar ratio of TiO2 to C is 1：4 and 1：5.In addition,fine TiC1.0 powders（D50 equals 3.04 μm） with single phase and low impurities are obtained when the molar ratio of TiO2 to C is 1：4.SEM observation shows that uniform shape,low agglomeration,and loose structure are observed on the surface of block product.

Thermodynamics and kinetics of carbothermal reduction of zinc ferrite by microwave heating

The kinetics of carbon reduction of ZnFe2O4 in the temperature range of 550-950 °C was investigated in a microwave tank-type reactor. The mechanism of formation of ZnO and Fe3O4/FeO by the decomposition of ZnFe2O4 was detailed using the equilibrium calculations and thermodynamics analysis by HSC chemistry software 6.0. In addition, the effects of decomposition temperature, the C/ZnFe2O4 ratio, the particle size and the microwave power were assessed on the kinetics of decomposition. Zn recovery as high as 97.93%could be achieved at a decomposition temperature of 750 °C with C/ZnFe2O4 ratio of 1：3, particle size of 61-74 μm and microwave power of 1200 W. The kinetics of decomposition was tested with different kinetic models and carbon gasification control mechanism was identified to be the appropriate mechanism. The activation energy for the carbon gasification reaction was estimated to be 38.21 kJ/mol.

Modified carbothermal reduction method for synthesis of LiFePO_4/C composite

With LiAc-2H2O as Li precursor,pure olivine phase LiFePO4/C was synthesized at a relatively low temperature（650 ℃） and short sintering period（4 h） by molten salt carbothermal reduction method.Scanning electron micrograph shows that particle size of the product is about 1μm,smaller than that of the sample synthesized with Li2CO3 as Li precursor.Electrochemical measurements prove that LiFePO4/C obtained from LiAc-2H2O shows high capacity.The initial discharge capacities are 148 mA-h/g at 0.5C rate and 115 mA-h/g at 5C rate,respectively.After 50 cycles,the capacity retention ratios are 93% and 89% at 0.5C rate and 5C rate,respectively.

Mineralogy and carbothermal reduction behaviour of vanadium-bearing titaniferous magnetite ore in Eastern India

Vanadium-beaxing titaniferous magnetite bands hosted by Precambrian gabbro-norite-anorthositic rocks or their metamorphic equivalents were discovered in some parts of Eastern Indian Shield, containing 48%-49% Fe （total）, 10%-25% TiO2, and 0.3%-2.20% V2O5 by mass. Mineralogical and petrological study, composition, and characterization of the vanadium-bearing titaniferous magnetite ore were carried out by scanning electron microscopy-energy dispersive X-ray （SEM-EDX）, wave length X-ray florescence （WDXRF）, inductively coupled plasma-atomic emission spectroscopy （ICP-AES）, X-ray diffraction （XRD）, etc. Chemical beneficiation for valuable metals, such as Fe, Ti, andV, was performed by reduction roasting. The direct and indirect reduction were investigated by mixing the lump ore with solid activated charcoal in a closed reactor and purging the reducing gas mixture in standard reducibility index apparatus at different temperatures and time intervals. The reduction roasting parameters were optimized. Finally, the reduced samples were crushed and upgraded by magnetic separation. The results show that, the maximum mass fractions of magnetic and nonmagnetic parts achieved axe 69.36% and 30.64%, respectively, which contain 10.6% TiO2 and 0.84% V205 in the magnetic part and 36.5% TiO2 and 0.22% V205 in the nonmagnetic part.

Preparation of titanium oxycarbide from various titanium raw materials:Part I.Carbothermal reduction

Carbothermal reduction was performed at temperatures up to 1600°C for vanadium-bearing titanomagnetite,ilmenite concentrate,and high titania slag.The possibility of selective carbothermal reduction was discussed in detail from the viewpoint of thermodynamics,and also tested.The products were analyzed by X-ray diffraction,scanning electron microscopy,and chemical analysis.The results show that it is possible to reduce all iron oxide to metallic iron,and titania to oxycarbide（TiCxOy）,without the reduction of other oxides like silica and magnesia.

Influence of chromium modification on the properties of MnO_x-FeO_x catalysts for the low-temperature selective catalytic reduction of NO by NH_3

Catalytic properties of MnOx-FeOx complex oxide （hereafter denoted as Mn-Fe） catalysts modified with different loadings of chromium oxide were investigated by using the combination of physico-cbemical techniques, such as N2 physisorption, X-ray diffraction （XRD）, high-resolution transmission electron microscope （HRTEM）, in situ Fourier transform infrared spectroscopy （in situ FT-IR） and temperature-programmed reduction （TPR） and their catalytic activities were evaluated with the selective catalytic reduction （SCR） of NOx by NH3. It was found that with the addition of Cr, more NO could be removed in the low-temperature window （below 120 ℃）. Among the tested catalysts, Mn-Fe- Cr （2 ： 2 ： 1） catalyst exhibited the best catalytic performance at 80 ℃ with the NO conversion higher than 90%. The combination of the reaction and characterization results indicated that （1） the strong interaction among tertiary metal oxides existed in the catalysts when Cr was appropriately added, which made the active components better dispersed with less agglomeration and sintering and the largest BET specific surface area could be obtained; （2） Cr improved the low-temperature reducibility of the catalyst and promoted the formation of the active intermediate （-NH3＋）, which favored the low-temperature SCR reaction.

Synthesis of novel MnO_x@TiO_2 core-shell nanorod catalyst for low-temperature NH_3-selective catalytic reduction of NOx with enhanced SO_2 tolerance

In this study,a MnOx@TiO2 core‐shell catalyst prepared by a two‐step method was used for the low‐temperature selective catalytic reduction of NOx with NH3.The catalyst exhibits high activity,high stability,and excellent N2 selectivity.Furthermore,it displays better SO2 and H2O tolerance than its MnOx,TiO2,and MnOx/TiO2 counterparts.The prepared catalyst was characterized systematically by transmission electron microscopy,high‐resolution transmission electron microscopy,X‐ray diffraction,Raman,BET,X‐ray photoelectron spectroscopy,NH3 temperature‐programmed desorption and H2 temperature‐programmed reduction analyses.The optimized MnOx@TiO2 catalyst exhibits an obvious core‐shell structure,where the TiO2 shell is evenly distributed over the MnOx nanorod core.The catalyst also presents abundant mesopores,Lewis‐acid sites,and high redox capability,all of which enhance its catalytic performance.According to the XPS results,the decrease in the number of Mn4+active centers after SO2 poisoning is significantly lower in MnOx@TiO2 than in MnOx/TiO2.The core‐shell structure is hence able to protect the catalytic active sites from H2O and SO2 poisoning.

Carbothermal reduction-chlorination-disproportionation of alumina in vacuum

The carbothermal reduction-chlorination-disproportionation of alumina in vacuum was investigated by XRD and thermodynamic analysis. The experiments on alumina and graphite at 1643-1843 K in vacuum were carried out. The results demonstrate that AlCl3（g） reacts with Al2O（g） or Al（g） generated from the carbothermal reduction of alumina to form AlCl（g）, and the AlCl（g） disproportionates to aluminum and AlCl3（g） at a lower temperature and the reaction rate of AlCl（g） reaches 90% at 980 K and 100 Pa. The aluminum can absorb CO to catalyze its disproportionation to C and CO2, and react backward with CO to form Al4C3, Al2O3, C and CO2, resulting in the aluminum product containing C, Al4C3 and Al2O3. The impurities in the aluminum product decrease as the AlCl（g） disproportionation temperature decreases. AlCl3 condenses at a temperature approximated to the room temperature.

Carbothermal reduction process of the Fe-Cr-O system

Understanding the reduction behaviors and characteristics of the end products of Fe-Cr-O systems is very important not only for maximizing the recovery of metals from stainless steel dust but also for the subsequent reuse in metallurgical process. The present work first predicted the possible products thermodynamically when FeCr204 was reduced by C. The reduction behaviors by graphite of three kinds of Fe-Cr-O systems, i.e., FeCr204, Fe203q-Cr203, and Feq-Cr203, were then investigated in 1350-1550℃. Further, the microstructures of final products and element distribution conditions were examined. The results suggest that, thermodynamically, the mass of products for the carbothermal reduction of FeCr204 is a strong function of temperature, and the initial carbon content is used. More Fe-Cr-C solution and less residual carbon content are obtained at higher temperatures and lower no：no ratios （the initial molar ratio of C to O in the sample）. Experimental data show that the sample amount tends to affect the reduction rate, and the residual carbon content strongly depends on nc：no. With regard to the phases present in products during the reaction process, metal carbides tend to form in the initial stage, whereas Fe-Cr-C solution forms when the degree of reduction is sufficiently high.

Production of magnesium during carbothermal reduction of magnesium oxide by differential condensation of magnesium and alkali vapours

Most of researchers believed that the developments on the condensation of magnesium produced by carbothermic reduction just concentrated on two process routes:the“quench”route and the“solvent”route.But this paper will briefly analyzes the major challenges in magnesium vapor condensation during the vacuum carbothermic reduction of calcined dolomite,on equipment upgrade,heat transfers alter,to achieve condensation control and production collection.Solutions are then proposed using theoretical calculations and experiment results.Comparative analysis of the experiment results shows that the burning and even explosion of condensation products during the vacuum carbothermic reduction of calcined dolomite are mainly due to the burning of crystallized powder magnesium,which results from the self-ignition of alkali metals.Finally,this paper proposes a multistage condensation solution to improve traditional vacuum condensation equipment.And result show that the condensation equipment can effectively mitigate the burning and loss during condensation,also the morphology of the condensation products clearly improved,the grain size increased,and the oxidation rate decreased.The potassium/sodium vapor and the magnesium vapor were separately condensed.

Effects of Technological Parameters on Carbothermal Reduction and Nitridation of Zircon

Carbothermal reduction and nitridation （CRN） of zircon （ ZrSiO4 ） permits obtaining diffbrent composites of oxides and nitrides such as ZrO2 -Si2N2O and ZrN - Si3N4. The effects tf technological parameters （ carbon source, reaction temperature, and carbon con.tent ） on the reaction rate and product phase composition of CRN of zircon were investigated by TGA and XRD. The resuhs show that： （1） carbon source is an important factor for a rapid reaction, and actiwtted carbon is chosen as the carbon source considering the expect products and reaction rate ; （ 2 ） reaction tetnperature has vital effect on reaction rate and product. In, case of carbon content above 20% , the zircon phase and m-ZrO2 phase decrease with increasing temperature, while the ZF7N8O4 phase increases firstly and then decreases, and the ZrN phase increases continually; （3） different carbon contents result in different reaction products. The higher the carbon content, the lower the starting temperature for the CRN of zircon.

TiO_2-Supported Binary Metal Oxide Catalysts for Low-temperature Selective Catalytic Reduction of NO_x with NH_3

Binary metal oxide（MnOx-A/TiO2）catalysts were prepared by adding the second metal to manganese oxides supported on titanium dioxide（TiO2）,where,A indicates Fe2O3,WO3,MoO3,and Cr2O3.Their catalytic activity,N2 selectivity,and SO2 poisonous tolerance were investigated.The catalytic performance at low temperatures decreased in the following order：Mn-W/TiO2〉Mn-Fe/TiO2〉Mn-Cr/TiO2〉Mn-Mo/TiO2,whereas the N2 selectivity decreased in the order：Mn-Fe/TiO2〉Mn-W/TiO2〉Mn-Mo/TiO2〉Mn-Cr/TiO2.In the presence of 0.01%SO2 and 6%H2O,the NOx conversions in the presence of Mn-W/TiO2,Mn-Fe/TiO2,or Mn-Mo/TiO2 maintain 98.5%,95.8%and 94.2%, respectively,after 8 h at 120°C at GHSV 12600 h？ 1 .As effective promoters,WO3 and Fe2O3 can increase N2 selectivity and the resistance to SO2 of MnOx/TiO2 significantly.The Fourier transform infrared（FTIR）spectra of NH3 over WO3 show the presence of Lewis acid sites.The results suggest that WO3 is the best promoter of MnOx/TiO2,and Mn-W/TiO2 is one of the most active catalysts for the low temperature selective catalytic reduction of NO with NH3.

Synthesis of titanium oxycarbonitride by carbothermal reduction and nitridation of ilmenite with recycling of polyethylene terephthalate (PET)

An innovative and sustainable carbothermal reduction and nitridation(CTRN) process of ilmenite(FeTiO_3) using a mixture of polyethylene terephthalate(PET) and coal as the primary reductant under an H_2–N_2 atmosphere was proposed. The use of PET as an alternative source of carbon not only enhances the porosity of the pellets but also results in the separation of Fe from titanium oxycarbonitride(TiOxCyNz) particles because of the differences in surface tension. The experiments were carried out at 1250°C for 3 h using four different PET contents ranging from 25wt% to 100wt% in the reductant. X-ray diffraction(XRD),scanning electron microscopy(SEM) in conjunction with energy-dispersive X-ray spectroscopy(EDX),and LECO elemental analysis were used to study the phases and microstructures of the reduced samples. In the case of 75wt% PET,iron distinctly separated from the synthesized Ti OxCyNz phase. With increasing PET content in the sample,the reduction and nitridation rates substantially increased. The synthesis of an oxycarbonitride with stoichiometry of TiO_(0.02)C_(0.13)N_(0.85) with minimal intermediate titanium sub-oxides was achieved. The results also showed that the iron particles formed from CTRN of FeTiO_3 exhibited a spherical morphology,which is conducive for Fe removal via the Becher process.

SYNTHESIS OF TiN BY MICROWAVE CARBOTHERMAL REDUCTION OF TiO_2

Titanium nitride powder was synthesized by microwave carbothermal reduction of titanium oxide. The mechanism and thermal dynamics of the reaction process were studied. The results show that the microwave carbothermal reduction technology has unique advantages over the conventional reduction methods. It can not only lower the reaction temperature, shorten the synthesis cycle, but also refine the product particles,as well as improving the reactivity of the powder.

Comparative evaluation of energy and resource consumption for vacuum carbothermal reduction and Pidgeon process used in magnesium production

With the fast development of the application of magnesium based alloys,the demand for primary magnesium is increasing dramatically all over the world.The Pidgeon process is the most widely used process for producing magnesium in China,but suffers from problems such as high energy,resource consumption and environmental pollution.While the process of vacuum carbothermal reduction to produce magnesium(VCTRM)has attracted more and more attention as its advantages,but it has not been well-practiced in industrial applications and there also is no comprehensive and quantitative analysis of this process.This study quantified the flows of resource and energy for the Pidgeon process and the VCTRM process,then compared and analyzed these two processes with each other from three aspects.The VCTRM process results in 63.14%and 69.16%lower of non-renewable mineral resources and energy consumptions when compared to the Pidgeon process,respectively.Moreover,the low energy consumption(2.675 tce vs.8.681 tce)and material to magnesium ratio(2.953:1 vs.6.429:1)of the VCTRM process,which lead to lower greenhouse gas(GHG)emissions(8.777 t vs.26.337 t)and solid waste generation(0.522 t vs.5.465 t)with a decrease of 66.67%and 90.45%,respectively.Results indicate that the VCTRM process is a more environmentally friendly process for magnesium production with high efficiency but low cost and low pollution,and it shows a good potential to be industrialized in the future after solving the bottleneck problem of the reverse reaction.

Response Surface Optimization for Process Parameters of LiFePO_4/C Preparation by Carbothermal Reduction Technology

A statistically based optimization strategy is used to optimize the carbothermal reduction technology for the synthesis of LiFePO4/C using LiOH,FePO4 and sucrose as raw materials.The experimental data for fitting the response are collected by the central composite rotatable design(CCD).A second order model for the discharge ca-pacity of LiFePO4/C is expressed as a function of sintering temperature,sintering time and carbon content.The ef-fects of individual variables and their interactions are studied by a statistical analysis(ANOVA).The results show that the linear effects and the quadratic effects of sintering temperature,carbon content and the interactions among these variables are statistically significant,while those effects of sintering time are insignificant.Response surface plots for spatial representation of the model illustrate that the discharge capacity depends on sintering temperature and carbon content more than sintering time.The model obtained gives the optimized reaction parameters of sinter-ing temperature at 652.0 ℃,carbon content of 34.33 g?mol-1 and 8.48 h sintering time,corresponding to a dis-charge capacity of 150.8 mA·h·g-1.The confirmatory test with these optimum parameters gives the discharge ca-pacity of 147.2 and 105.1 mA·h·g-1 at 0.5 and 5 C,respectively.

Synthesis of ZrO_2-SiC Composite by Carbothermal Reduction of Zircon

Zircon （mesh size ≤ 44μm ） and carbon black （mesh size ≤30μm ） were used as the starting materials, weighed with re（zircon） ： re（carbon black） of 100 ： 20 and mixed fully. The specimens with the diameter of 20ram and length of 5ram were prepared by pressing at 100 MPa, then dried at 120℃ for 12h, put into a furnace with 1. 5L ·min^-1 argon gas and fired at 1450℃, 1500℃, 1550℃, 1600℃ and 1650℃ for 4h, respectively. The chemical composition, phase composition and microstructure of the specimens were studied by chemical analysis, X-ray diffraction and scanning electronic microscope, and the carbothermal reduction reaction process was discussed by thermodynamic analysis. The results showed that the ZrO2-SiC composite could be synthesized by carbothermal reduction reaction using zircon and carbon black as the starting materials in argon atmosphere. The composite with different composition was obtained by controlling the firing temperature and partial pressure of CO gas. The proper temperature to synthesize ZrO2-SiC composite was 1600℃ in this experiment.