Currently,the carbothermal reduction-nitridation(CRN)process is the predominant method for preparing aluminum nitride(AlN)powder.Although AlN powder prepared by CRN process exhibits high purity and excellent sintering...Currently,the carbothermal reduction-nitridation(CRN)process is the predominant method for preparing aluminum nitride(AlN)powder.Although AlN powder prepared by CRN process exhibits high purity and excellent sintering activity,it also presents challenges such as the necessity for high reaction temperatures and difficulties in achieving uniform mixing of its raw materials.This study presents a comprehensive investigation into preparation process of AlN nanopowders using a combination of hydrothermal synthesis and CRN.In the hydrothermal reaction,a homogeneous composite precursor consisting of carbon and boehmite(γ-AlOOH)is synthesized at 200℃using aluminum nitrate as the aluminum source,sucrose as the carbon source,and urea as the precipitant.During the hydrothermal process,the precursor develops a core-shell structure,with boehmite tightly coated with carbon(γ-AlOOH@C)due to electrostatic attraction.Compared with conventional precursor,the hydrothermal hybrid offers many advantages,such as ultrafine particles,uniform particle size distribution,good dispersion,high reactivity,and environmental friendliness.The carbon shell enhances thermodynamic stability of γ-Al_(2)O_(3) compared to the corundum phase(α-Al_(2)O_(3))by preventing the loss of the surface area in alumina.This stability enables γ-Al_(2)O_(3) to maintain high reactivity during CRN process,which initiates at 1300℃,and concludes at 1400℃.The underlying mechanisms are substantiated through experiments and thermodynamic calculations.This research provides a robust theoretical and experimental foundation for the hydrothermal combined carbothermal preparation of non-oxide ceramic nanopowders.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 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
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
(Ca, Mg)-α′-Sialon-AlN-BN powders were synthesized by the carbothermal reduction and nitridation (CRN) method using boron-rich slag, one of the intermediate products from pyrometallurgy separation of pageit, as the ...(Ca, Mg)-α′-Sialon-AlN-BN powders were synthesized by the carbothermal reduction and nitridation (CRN) method using boron-rich slag, one of the intermediate products from pyrometallurgy separation of pageit, as the staring material. The influences of synthesis temperature and holding time on the phase composition and microstructure during the microwave CRN were studied by XRD, SEM and EDS. The comparison between two heating techniques, conventional and microwave heating, on the synthesized powder was presented as well. The experimental results revealed that the phase compositions and microstructures of the synthesized products were greatly affected by the synthesis temperature and holding time. With an increase in the synthesis temperature or holding time, the relative amount of α′-Sialon increased and α′-Sialon became the main crystalline phase at 1400 °C for 6 h. The synthesized products also contained AlN, BN and a small amount of β-SiC. Elongated α′-Sialon grains, short rod AlN grains, aggregate nanoscale BN grains were observed in the synthesized powders. The reaction temperature of microwave heating method was reduced by 80 °C, the reaction time was shortened by 2 h, and more elongated α′-Sialon grains with large aspect ratio were observed.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
A new approach to the massive production of TiC whiskers with high purity and low cost was presented. It is a modified carbothermal reduction method （MCTR） characterized by argon stream flowing vertically and passin...A new approach to the massive production of TiC whiskers with high purity and low cost was presented. It is a modified carbothermal reduction method （MCTR） characterized by argon stream flowing vertically and passing through the interior of the mixture of raw materials. It is found for the first time that there is an optimum flow of the upward flowing argon stream, at which large quantity of high quality TiC can be obtained. This paper described the new method, analyzed the mechanism and conditions for the formation of high purity TiC whiskers on a large scale, and compared MCTR with the traditional carbothermal reduction method （TCTR）. Based on the analysis and comparison, it is concluded that in order to produce high quality transition metal carbides, nitrides and carbonitrides with low cost TCTR must be replaced by MCTR.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
The porous spherical LiFePO4/C powders were prepared by spray drying and carbothermal method （SDCTM）. Cheaper trivalent iron ion was used as the precursor. The pure olivine phase can be prepared with the spray dryin...The porous spherical LiFePO4/C powders were prepared by spray drying and carbothermal method （SDCTM）. Cheaper trivalent iron ion was used as the precursor. The pure olivine phase can be prepared with the spray drying and subsequent heat-treatment. The average particle size is around 10μm, and the value of porosity is 63.04%. The results indicate that the initial discharge capacity decreases with increasing charge/ discharge rate and reduces from 138.8 mAh · g^-1 at C/20 rate to 98.3 mAh ·g^-1 at 2C rate, while the polarization between the charge and discharge plateaux is enlarged from 53 mv to 347 mv. However, the average discharge efficiency is up to 99.5% at 2C rate compared to 80.6% at C/20 rate from the second cycle.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
In view of the difficulty of extracting iron from Bayer red mud,a new idea of adding laterite nickel ore into red mud was proposed to prepare a high value-added product.Toward this,the influences of laterite nickel or...In view of the difficulty of extracting iron from Bayer red mud,a new idea of adding laterite nickel ore into red mud was proposed to prepare a high value-added product.Toward this,the influences of laterite nickel ore on thermodynamic reaction,slagging and smelting reduction of extracting iron from red mud were studied.The results indicated that the product of extracting iron from red mud(R100)was changed with the addition of laterite nickel ore(R70L30).The slag of R100 was strongly basic,while the R70L30 was weakly acidic with composition closer to the ideal blast furnace slag.The metal recovery of R100 was 75.16%and that of R70L30 was 94.05%.At the same temperature,the slag viscosity of R70L30 was significantly lower than that of R100,which proved that laterite nickel ore can adjust the basicity,reduce melting point of slag and improve metal recovery.Because Fe,Ni and Cr in red mud and laterite nickel ore can be reduced sufficiently,a low Ni–Cr alloy cast iron can be directly prepared.展开更多
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...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.展开更多
基金National Key Research and Development Program of China(2022YFB3708500,2023YFB3611000)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2020ZZ109)。
文摘Currently,the carbothermal reduction-nitridation(CRN)process is the predominant method for preparing aluminum nitride(AlN)powder.Although AlN powder prepared by CRN process exhibits high purity and excellent sintering activity,it also presents challenges such as the necessity for high reaction temperatures and difficulties in achieving uniform mixing of its raw materials.This study presents a comprehensive investigation into preparation process of AlN nanopowders using a combination of hydrothermal synthesis and CRN.In the hydrothermal reaction,a homogeneous composite precursor consisting of carbon and boehmite(γ-AlOOH)is synthesized at 200℃using aluminum nitrate as the aluminum source,sucrose as the carbon source,and urea as the precipitant.During the hydrothermal process,the precursor develops a core-shell structure,with boehmite tightly coated with carbon(γ-AlOOH@C)due to electrostatic attraction.Compared with conventional precursor,the hydrothermal hybrid offers many advantages,such as ultrafine particles,uniform particle size distribution,good dispersion,high reactivity,and environmental friendliness.The carbon shell enhances thermodynamic stability of γ-Al_(2)O_(3) compared to the corundum phase(α-Al_(2)O_(3))by preventing the loss of the surface area in alumina.This stability enables γ-Al_(2)O_(3) to maintain high reactivity during CRN process,which initiates at 1300℃,and concludes at 1400℃.The underlying mechanisms are substantiated through experiments and thermodynamic calculations.This research provides a robust theoretical and experimental foundation for the hydrothermal combined carbothermal preparation of non-oxide ceramic nanopowders.
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 (2006AA06Z368) supported by High-tech Research and Development Programs of ChinaProject (N100402007) supported by the Fundamental Research Funds for the Central Universities in China
文摘(Ca, Mg)-α′-Sialon-AlN-BN powders were synthesized by the carbothermal reduction and nitridation (CRN) method using boron-rich slag, one of the intermediate products from pyrometallurgy separation of pageit, as the staring material. The influences of synthesis temperature and holding time on the phase composition and microstructure during the microwave CRN were studied by XRD, SEM and EDS. The comparison between two heating techniques, conventional and microwave heating, on the synthesized powder was presented as well. The experimental results revealed that the phase compositions and microstructures of the synthesized products were greatly affected by the synthesis temperature and holding time. With an increase in the synthesis temperature or holding time, the relative amount of α′-Sialon increased and α′-Sialon became the main crystalline phase at 1400 °C for 6 h. The synthesized products also contained AlN, BN and a small amount of β-SiC. Elongated α′-Sialon grains, short rod AlN grains, aggregate nanoscale BN grains were observed in the synthesized powders. The reaction temperature of microwave heating method was reduced by 80 °C, the reaction time was shortened by 2 h, and more elongated α′-Sialon grains with large aspect ratio were observed.
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.
文摘A new approach to the massive production of TiC whiskers with high purity and low cost was presented. It is a modified carbothermal reduction method （MCTR） characterized by argon stream flowing vertically and passing through the interior of the mixture of raw materials. It is found for the first time that there is an optimum flow of the upward flowing argon stream, at which large quantity of high quality TiC can be obtained. This paper described the new method, analyzed the mechanism and conditions for the formation of high purity TiC whiskers on a large scale, and compared MCTR with the traditional carbothermal reduction method （TCTR）. Based on the analysis and comparison, it is concluded that in order to produce high quality transition metal carbides, nitrides and carbonitrides with low cost TCTR must be replaced by MCTR.
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.
文摘The porous spherical LiFePO4/C powders were prepared by spray drying and carbothermal method （SDCTM）. Cheaper trivalent iron ion was used as the precursor. The pure olivine phase can be prepared with the spray drying and subsequent heat-treatment. The average particle size is around 10μm, and the value of porosity is 63.04%. The results indicate that the initial discharge capacity decreases with increasing charge/ discharge rate and reduces from 138.8 mAh · g^-1 at C/20 rate to 98.3 mAh ·g^-1 at 2C rate, while the polarization between the charge and discharge plateaux is enlarged from 53 mv to 347 mv. However, the average discharge efficiency is up to 99.5% at 2C rate compared to 80.6% at C/20 rate from the second cycle.
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financially supported by the Center of Ecological Collaborative Innovation for Aluminum Industry in Guangxi and the Special Project for Innovation-driven Development of Guangxi(No.AA17202001).
文摘In view of the difficulty of extracting iron from Bayer red mud,a new idea of adding laterite nickel ore into red mud was proposed to prepare a high value-added product.Toward this,the influences of laterite nickel ore on thermodynamic reaction,slagging and smelting reduction of extracting iron from red mud were studied.The results indicated that the product of extracting iron from red mud(R100)was changed with the addition of laterite nickel ore(R70L30).The slag of R100 was strongly basic,while the R70L30 was weakly acidic with composition closer to the ideal blast furnace slag.The metal recovery of R100 was 75.16%and that of R70L30 was 94.05%.At the same temperature,the slag viscosity of R70L30 was significantly lower than that of R100,which proved that laterite nickel ore can adjust the basicity,reduce melting point of slag and improve metal recovery.Because Fe,Ni and Cr in red mud and laterite nickel ore can be reduced sufficiently,a low Ni–Cr alloy cast iron can be directly prepared.
基金financial support from Universiti Sains Malaysia(USM)Fellowship(APEX 1002/JHEA/ATSG4001)financially supported by USM and Ministry of Higher Education(MOHE)of Malaysia through Fundamental Research Grant Scheme(FRGS)(Nos.203/PBAHAN/6071230 and 203/PBAHAN/607126)Research University Grant for Individual(RUI)from USM(No.1001/PBAHAN/814273)
文摘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.
