The increasing demand for magnesium as a next-generation structural material highlights the significance of incorporating CaF_(2)as a catalyst to enhance the efficiency of vacuum carbothermal reduction of magnesium(VC...The increasing demand for magnesium as a next-generation structural material highlights the significance of incorporating CaF_(2)as a catalyst to enhance the efficiency of vacuum carbothermal reduction of magnesium(VCTRM).This study investigates the thermodynamic theory and catalytic mechanism of CaF_(2)in the VCTRM process.Catalytic reduction experiments and molecular dynamics simulations were conducted to gain a comprehensive understanding of the process.Thermodynamic calculations indicate that in vacuum carbothermal reduction,the primary reaction occurs between MgO and C.Analysis shows that CaF_(2)'s catalytic action primarily involves F^(-),Ca^(2+),and melt eutectic.Our experiments demonstrate that the addition of CaF_(2)significantly increases the reduction rate.Furthermore,the mass loss rate increases with both the quantity of CaF_(2)added and the holding time,stabilizing at additions over 5%.Experiments conducted at temperatures above the melting point of CaF_(2)exhibited a pronounced catalytic effect.The resultant magnesium showed optimal structure and crystallization,with a purity of 87.84%.Notably,while CaF_(2)remained in the residue,it was not detected in the condensate,confirming its catalytic role.Molecular dynamics simulations revealed that molten CaF_(2)sabotages the structure of magnesium oxide,with F^(-)dispersing onto the surface of MgO,thus enhancing the reaction between MgO and C to form CO.However,no chemical reaction was observed between C,MgO,and CaF_(2).The occurrence of the carbothermal reduction reaction at high temperatures depends on the concentration of the reducing agent C,with CaF_(2)influencing the reaction rate.This research elucidates the theoretical and mechanistic foundations of CaF_(2)-catalyzed VCTRM,aligning with the green energy-saving concept and significantly advancing the green and efficient VCTRM process.展开更多
Resource utilization of metallurgical solid waste is vital for the sustainable development of the steel industry in the context of“dual carbon.”The calcification-carbothermal reduction method was employed to extract...Resource utilization of metallurgical solid waste is vital for the sustainable development of the steel industry in the context of“dual carbon.”The calcification-carbothermal reduction method was employed to extract zinc and iron from electric furnace dust effectively.In this process,calcium oxide reacts with zinc ferrite to form dicalcium ferrite and zinc oxide,which further promotes the effective separation of zinc and iron.However,the addition of pure calcium oxide increases production costs for steel companies.Herein,a new process for dust removal and zinc recovery in electric furnaces has been developed,using electric furnace slag as a calcium agent and mineral trough ash as a reducing agent.Large amounts of dicalcium ferrate phases were detected in the carbothermal reduction products by steel slag synergistic calcification.The reaction mechanism was determined as ZnFe_(2)O_(4)+CaO→Ca_(2)Fe_(2)O_(5)+ZnO→Ca_(2)Fe_(2)O_(5)+Zn(g).Such a two-step reaction path indicated that steel slag can effectively promote the reduction and volatilization of zinc.The experimental optimal roasting parameters were determined as roasting temperature of 1150℃,roasting time of 45 min,calcium to zinc molar ratio of 1.1,and carbon to oxygen molar ratio of 0.8.The mass percentage of added steel slag was recorded as 21.83%,while that of mineral trough ash was 21.85%.Under these conditions,the zinc removal rate above 99%and the metallization rate of pellets of about 75.31%were achieved.Overall,the proposed method looks promising for future efficient separation of zinc and iron in industrial steel slag.展开更多
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 th...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.展开更多
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 ZnFe2O...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.展开更多
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 mi...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.展开更多
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 （to...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.展开更多
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 ...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.展开更多
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. Th...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.展开更多
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 m...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.展开更多
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 r...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.展开更多
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 ...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.展开更多
The effects of mechanical activation on particle size distribution,crystalline phase,morphology,and mechanical energy storage of nickel slag were studied.Then,the direct reduction experiments of mechanically activated...The effects of mechanical activation on particle size distribution,crystalline phase,morphology,and mechanical energy storage of nickel slag were studied.Then,the direct reduction experiments of mechanically activated nickel slag mixed with reducing agent graphite powder were performed under conditions of 873-1273 K and reduction for 30-70 min.The results show that after 12 h of activation,90%of the nickel slag has a particle diameter less than 1.05 pm,and the total energy storage is 1790.4 kJ mol^(-1).With the extension of the mechanical activation duration,the intensity of the dift'raction peaks of the main crystalline phases Fe_(2)SiO_(4) and Mg2SiO4 in the nickel slag decreases.Mechanical activation is also an effective means to enhance the reduction of nickel slag.With the extension of the activation time,the reduction effect of the nickel slag and metallization degree increase.After 12 h of mechanical activation,the nickel slag was reduced at 1273 K for 70 min,and the metallization degree of the reduced product could reach 83.12%.展开更多
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 （ carb...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.展开更多
Using boron powder as additive, the preparation of zirconium diboride(ZrB 2) by carbothermal reduction was investigated. The results show that the carbothermal reduction cannot be completely done until the temperature...Using boron powder as additive, the preparation of zirconium diboride(ZrB 2) by carbothermal reduction was investigated. The results show that the carbothermal reduction cannot be completely done until the temperature is more than 1900 ℃. The ZrB2 particles prepared without boron(B) additive at 1900 ℃ for 3 h are rodlike and show a preferential grain growth along [001] direction. B additive changes the heat effect of the raw materials. With B additive, the morphology of ZrB2 particles turns to be regular shape. The average particle size is about 3.6 μm with 2.5 wt% B additives. With more B additive, the shape of particles turns to be round like and the average particle size is decreased to 2.3 μm when 5 wt% B is added. The existence of oxides in grain boundary is a key factor to keep ZrB2 ceramic from deep densification. Using ZrB2 powder prepared with 5 wt% B additives, by controlling carbon content in ZrB2 powder, ZrB2 ceramic with 93%relative density is hot-pressed.展开更多
For the purpose of exploring a potential process to produce FeMn,the effects of microwave heating on the carbothermal reduction characteristics of oxidized Mn ore was investigated.The microwave heating curve of the mi...For the purpose of exploring a potential process to produce FeMn,the effects of microwave heating on the carbothermal reduction characteristics of oxidized Mn ore was investigated.The microwave heating curve of the mixture of oxidized Mn ore and coke was analyzed in association with the characterization of dielectric properties.The comparative experiments were conducted on the carbothermal reductions through conventional and microwave heatings at temperatures ranging from 973 to 1373 K.The thermogravimetric analysis showed that carbothermal reactions under microwave heating proceeded to a greater extent and at a faster pace compared with those under conventional heating.The metal phases were observed in the microstructures only under microwave heating.The carbothermal reduction process under microwave heating was discussed.The electric and magnetic susceptibility differences were introduced into the thermodynamics analysis for the formation of metal Mn.The developed thermodynamics considered that microwave heating could make the reduction of MnO to Mn more accessible and increase the reduction extent.展开更多
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 ...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.展开更多
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) substrat...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.展开更多
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...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.展开更多
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...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%.展开更多
The carbothermal reduction of MgO and Al_(2)O_(3) in argon flow at low pressure allows to lower the onset temperature of metal vapor formation.Thermodynamic calculations indicate that metal formation begins at 1400 an...The carbothermal reduction of MgO and Al_(2)O_(3) in argon flow at low pressure allows to lower the onset temperature of metal vapor formation.Thermodynamic calculations indicate that metal formation begins at 1400 and 1700 K for a primary vacuum(1000 Pa),respectively,for Mg and Al.In the experimental section,concentrated solar energy was used for the process heating in order to favor energy savings.The products of the reaction between MgO or Al_(2)O_(3) and 2 varieties of carbon(graphite,carbon black)in flowing argon atmosphere at a total pressure of around 1000 to 1600 Pa were studied using X-ray diffraction,and microstructure observations revealed the formation of metallic nanopowders with some by-products.Metallic conversions close to 45 wt%and 52 wt%,respectively,for Mg and Al,were obtained.The low conversion yield of the carbothermal reduction of MgO can be attributed to a backward reaction reforming MgO powder and to a sintering process between oxide particles at high temperature.Aluminum production challenge is to avoid formation of undesired by-products:Al_(2)O,Al_(4)C_(3) and Al-oxycarbides.Advantages and weaknesses of the used process are described and some improvements are proposed to increase metallic yields.展开更多
基金supported by the Leading Talents of Industrial Technology in Yunnan Province[grant number 618820190024]the Yunnan Province Nonferrous Metal Vacuum Metallurgy Top Team[grant number 202305AS350012].
文摘The increasing demand for magnesium as a next-generation structural material highlights the significance of incorporating CaF_(2)as a catalyst to enhance the efficiency of vacuum carbothermal reduction of magnesium(VCTRM).This study investigates the thermodynamic theory and catalytic mechanism of CaF_(2)in the VCTRM process.Catalytic reduction experiments and molecular dynamics simulations were conducted to gain a comprehensive understanding of the process.Thermodynamic calculations indicate that in vacuum carbothermal reduction,the primary reaction occurs between MgO and C.Analysis shows that CaF_(2)'s catalytic action primarily involves F^(-),Ca^(2+),and melt eutectic.Our experiments demonstrate that the addition of CaF_(2)significantly increases the reduction rate.Furthermore,the mass loss rate increases with both the quantity of CaF_(2)added and the holding time,stabilizing at additions over 5%.Experiments conducted at temperatures above the melting point of CaF_(2)exhibited a pronounced catalytic effect.The resultant magnesium showed optimal structure and crystallization,with a purity of 87.84%.Notably,while CaF_(2)remained in the residue,it was not detected in the condensate,confirming its catalytic role.Molecular dynamics simulations revealed that molten CaF_(2)sabotages the structure of magnesium oxide,with F^(-)dispersing onto the surface of MgO,thus enhancing the reaction between MgO and C to form CO.However,no chemical reaction was observed between C,MgO,and CaF_(2).The occurrence of the carbothermal reduction reaction at high temperatures depends on the concentration of the reducing agent C,with CaF_(2)influencing the reaction rate.This research elucidates the theoretical and mechanistic foundations of CaF_(2)-catalyzed VCTRM,aligning with the green energy-saving concept and significantly advancing the green and efficient VCTRM process.
基金the support from Graduate Student Scientific Research Innovation Projects in Jiangsu Province(KYCX22_3804)Natural Science Foundation of Jiangsu Province(No.BK20210888).
文摘Resource utilization of metallurgical solid waste is vital for the sustainable development of the steel industry in the context of“dual carbon.”The calcification-carbothermal reduction method was employed to extract zinc and iron from electric furnace dust effectively.In this process,calcium oxide reacts with zinc ferrite to form dicalcium ferrite and zinc oxide,which further promotes the effective separation of zinc and iron.However,the addition of pure calcium oxide increases production costs for steel companies.Herein,a new process for dust removal and zinc recovery in electric furnaces has been developed,using electric furnace slag as a calcium agent and mineral trough ash as a reducing agent.Large amounts of dicalcium ferrate phases were detected in the carbothermal reduction products by steel slag synergistic calcification.The reaction mechanism was determined as ZnFe_(2)O_(4)+CaO→Ca_(2)Fe_(2)O_(5)+ZnO→Ca_(2)Fe_(2)O_(5)+Zn(g).Such a two-step reaction path indicated that steel slag can effectively promote the reduction and volatilization of zinc.The experimental optimal roasting parameters were determined as roasting temperature of 1150℃,roasting time of 45 min,calcium to zinc molar ratio of 1.1,and carbon to oxygen molar ratio of 0.8.The mass percentage of added steel slag was recorded as 21.83%,while that of mineral trough ash was 21.85%.Under these conditions,the zinc removal rate above 99%and the metallization rate of pellets of about 75.31%were achieved.Overall,the proposed method looks promising for future efficient separation of zinc and iron in industrial steel slag.
基金Project(u0837604)supported by the Natural Science Foundation of Yunnan Province,ChinaProject(51004058)supported by the National Natural Science Foundation of ChinaProject(20095314110003)supported by Specialized Research Fund for the Doctoral Program of Higher Education
文摘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.
基金Projects (51004059,E041601) supported by the National Natural Science Foundation of ChinaProject (14051157) supported by Natural Science Foundation of Yunnan Province
文摘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.
基金Project(21001041) supported by the National Natural Science Foundation of ChinaProject(102300410256) supported by Henan Province Foundation and Advanced Technology Research Program,China+1 种基金Project(102102210183) supported by the Key Scientific and Technological Research Project of Henan Province,ChinaProject(2011B480005) supported by the Natural Science Research Project of Henan Province,China
文摘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.
基金the financial support from the Ministry of Steel SDF Project,the Government of India
文摘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.
基金supported by the National Natural Science Foundation of China (No.50574012)
文摘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.
基金Project (u0837604) supported by the Joint Funds of the National Natural Science Foundation of China and Yunnan Province
文摘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.
基金the Yunnan Ten Thousand Talents Plan Industrial Technology Champion Project Foundation of China(No.YNWR-CYJS-2018-015)Basic Research Project of Yunnan Province(No.2019FB080).
文摘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.
基金financially supported by the National Natural Science Foundation of China(No.51074025)the Fundamental Research Funds for the Central Universities of China(No.FRF-SD-12-009A)
文摘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.
基金Supported by the National Natural Science Foundation of China (50474092)GXNSFA (2011GXNSFA018015)
文摘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.
基金the National Natural Science Foundation of China(No.51774224)for the funding of this research.
文摘The effects of mechanical activation on particle size distribution,crystalline phase,morphology,and mechanical energy storage of nickel slag were studied.Then,the direct reduction experiments of mechanically activated nickel slag mixed with reducing agent graphite powder were performed under conditions of 873-1273 K and reduction for 30-70 min.The results show that after 12 h of activation,90%of the nickel slag has a particle diameter less than 1.05 pm,and the total energy storage is 1790.4 kJ mol^(-1).With the extension of the mechanical activation duration,the intensity of the dift'raction peaks of the main crystalline phases Fe_(2)SiO_(4) and Mg2SiO4 in the nickel slag decreases.Mechanical activation is also an effective means to enhance the reduction of nickel slag.With the extension of the activation time,the reduction effect of the nickel slag and metallization degree increase.After 12 h of mechanical activation,the nickel slag was reduced at 1273 K for 70 min,and the metallization degree of the reduced product could reach 83.12%.
基金the Natural Science Foundation of The Education Department of Henan Province,No.2011B430011the SRTP of Henan University of Science and Technology
文摘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.
基金financially supported by the National Natural Science Foundation of China(No. 51674035)
文摘Using boron powder as additive, the preparation of zirconium diboride(ZrB 2) by carbothermal reduction was investigated. The results show that the carbothermal reduction cannot be completely done until the temperature is more than 1900 ℃. The ZrB2 particles prepared without boron(B) additive at 1900 ℃ for 3 h are rodlike and show a preferential grain growth along [001] direction. B additive changes the heat effect of the raw materials. With B additive, the morphology of ZrB2 particles turns to be regular shape. The average particle size is about 3.6 μm with 2.5 wt% B additives. With more B additive, the shape of particles turns to be round like and the average particle size is decreased to 2.3 μm when 5 wt% B is added. The existence of oxides in grain boundary is a key factor to keep ZrB2 ceramic from deep densification. Using ZrB2 powder prepared with 5 wt% B additives, by controlling carbon content in ZrB2 powder, ZrB2 ceramic with 93%relative density is hot-pressed.
基金This work was financially supported by the National Natural Science Foundation of China(No.51704083).
文摘For the purpose of exploring a potential process to produce FeMn,the effects of microwave heating on the carbothermal reduction characteristics of oxidized Mn ore was investigated.The microwave heating curve of the mixture of oxidized Mn ore and coke was analyzed in association with the characterization of dielectric properties.The comparative experiments were conducted on the carbothermal reductions through conventional and microwave heatings at temperatures ranging from 973 to 1373 K.The thermogravimetric analysis showed that carbothermal reactions under microwave heating proceeded to a greater extent and at a faster pace compared with those under conventional heating.The metal phases were observed in the microstructures only under microwave heating.The carbothermal reduction process under microwave heating was discussed.The electric and magnetic susceptibility differences were introduced into the thermodynamics analysis for the formation of metal Mn.The developed thermodynamics considered that microwave heating could make the reduction of MnO to Mn more accessible and increase the reduction extent.
文摘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.
基金supported by the National Natural Science Foundation of China under Grant 62104024, Grant 11875097, Grant 12075045, Grant 11975257, Grant 11961141014, and Grant 62074146the Fundamental Research Funds for the Central Universities under Grant DUT19RC (3)074the Natural Science Foundation of Liaoning Province under Grant 2021MS124, Grant 2022020474JH2/1013。
文摘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.
文摘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.
基金supported by National Natural Science Foundation of China(52172031 and 51872266)Henan Provincial Science and Technology Research Project(222102230030).
文摘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%.
基金the Programme“Investissements d’Avenir”(Investment for the Future)of the Agence Nationale de la Recherche(National Agency for Research)of the French State under award number ANR-10-LABX-22-01-SOLSTICE through the funding of the post-doctoral position of J.Puig.
文摘The carbothermal reduction of MgO and Al_(2)O_(3) in argon flow at low pressure allows to lower the onset temperature of metal vapor formation.Thermodynamic calculations indicate that metal formation begins at 1400 and 1700 K for a primary vacuum(1000 Pa),respectively,for Mg and Al.In the experimental section,concentrated solar energy was used for the process heating in order to favor energy savings.The products of the reaction between MgO or Al_(2)O_(3) and 2 varieties of carbon(graphite,carbon black)in flowing argon atmosphere at a total pressure of around 1000 to 1600 Pa were studied using X-ray diffraction,and microstructure observations revealed the formation of metallic nanopowders with some by-products.Metallic conversions close to 45 wt%and 52 wt%,respectively,for Mg and Al,were obtained.The low conversion yield of the carbothermal reduction of MgO can be attributed to a backward reaction reforming MgO powder and to a sintering process between oxide particles at high temperature.Aluminum production challenge is to avoid formation of undesired by-products:Al_(2)O,Al_(4)C_(3) and Al-oxycarbides.Advantages and weaknesses of the used process are described and some improvements are proposed to increase metallic yields.
