The oxidation behaviors of AZ80,AZ8O-0.32 Y and AZ8O-0.38 Nd(wt.%)alloys were researched at 413℃,420℃,427v and 433℃for up to 6 h in air environment via a high precision analytical balance,a laser confocal microscop...The oxidation behaviors of AZ80,AZ8O-0.32 Y and AZ8O-0.38 Nd(wt.%)alloys were researched at 413℃,420℃,427v and 433℃for up to 6 h in air environment via a high precision analytical balance,a laser confocal microscope,differential scanning calorimeter(DSC)analysis,X-ray diffraction(XRD)analysis,scanning electron microscope(SEM)observation,and X-ray photoelectron spectroscopy(XPS)analysis.The results show that the weight gain and oxidation rate of AZ80 are reduced significantly,the initiation form and propagation of cracks in oxide layer are changed.Compact and protective oxide layer forms on alloy surface with Y or Nd addition.And the activation energies of AZ80,AZ80-0.32Y and AZ8O-0.38Nd alloys calculated via Arrhenius equation are 82.556 kJ/mol,177.148kJ/mol and 136.738 kJ/mol,respectively.展开更多
The oxidation pathway and kinetics of titania slag powders in air were analyzed using differential scanning calorimetry(DSC)and thermogravimetry(TG).The oxidation pathway of titania slag powder in air was divided into...The oxidation pathway and kinetics of titania slag powders in air were analyzed using differential scanning calorimetry(DSC)and thermogravimetry(TG).The oxidation pathway of titania slag powder in air was divided into three stages according to their three exothermic peaks and three corresponding mass gain stages indicated by the respective non-isothermal DSC and TG curves.The isothermal oxidation kinetics of high titania slag powders of different sizes were analyzed using the ln-ln analysis method.The results revealed that the entire isothermal oxidation process comprises two stages.The kinetic mechanism of the first stage can be described as f(α) = 1.77(1-α) [-ln (1-α)]^((1.77-1)/1.77),f(α)= 1.97(1-α) [-ln (1-α)]^((1.97-1)/1.97),and f (α) = 1.18(1-α) [-ln (1-α)]^((1.18-1)/1.18).The kinetic mechanism of the second stage for all samples can be described as f (α)=1.5(1-α)^(2/3)[1-(1-α)^(1/3)]^(-1).The activation energies of titania slag powders with different sizes(d_(1)<0.075 mm,0.125 mm<d_(2)<0.150 mm,and 0.425 mm<d_(3)<0.600 mm)for different reaction degrees were calculated.For the given experimental conditions,the rate-controlling step in the first oxidation stage of all the samples is a chemical reaction.The rate-controlling steps of the second oxidation stage are a chemical reaction and internal diffusion(for powders d_(1)<0.075 mm)and internal diffusion(for powders 0.125 mm<d_(2)<0.150 mm and 0.425 mm<d_(3)<0.600 mm).展开更多
The kinetic behavior of leaching copper from low grade copper oxide ore was investigated. The effects of leaching temperature, H2SO4 concentration, particle size of crude ore and agitation rate on the leaching efficie...The kinetic behavior of leaching copper from low grade copper oxide ore was investigated. The effects of leaching temperature, H2SO4 concentration, particle size of crude ore and agitation rate on the leaching efficiency of copper were also evaluated. And the kinetic equations of the leaching process were obtained. The results show that the leaching process can be described with a reaction model of shrinking core. The reaction can be divided into three stages. The first stage is the dissolution of free copper oxide and copper oxide wrapped by hematite-limonite ore. At this stage, the leaching efficiency is very fast （leaching efficiency is larger than 60%）. The second stage is the leaching of diffiuent copper oxides, whose apparent activation energy is 43.26 kJ/mol. During this process, the chemical reaction is the control step, and the reaction order of H2SO4 is 0.433 84. The third stage is the leaching of copper oxide wrapped by hematite-limonite and silicate ore with apparent activation energy of 16.08 kJ/mol, which belongs to the mixed control.展开更多
Clay samples containing 8.15% iron oxides and 27.49% alumina were leached in oxalic acid. Leaching experiments were per-formed in aqueous solutions of oxalic acid of 0.2-2 mol/L at 40-80 C for up to 90 min. The mixed ...Clay samples containing 8.15% iron oxides and 27.49% alumina were leached in oxalic acid. Leaching experiments were per-formed in aqueous solutions of oxalic acid of 0.2-2 mol/L at 40-80 C for up to 90 min. The mixed kinetic mechanism, i.e., t/τ=[（1 2X/3） （1 X）2/3 ]＋b[ 1 （1 X）1/3], seemed to be the most appropriate one to fit the kinetic data of leaching iron oxides contained in clay in the aqueous oxalic acid solutions. The Arrhenius activation energy for leaching in the 1.8 mol/L oxalic acid was found to be 41.035 kJ/mol.展开更多
The oxidation of carbon nanotubes, C60 and graphite was studied by thermogravimetric (TG) analysis and differential thermal analysis (DTA) technique, and the oxidation kinetic models of three carbon materials studied ...The oxidation of carbon nanotubes, C60 and graphite was studied by thermogravimetric (TG) analysis and differential thermal analysis (DTA) technique, and the oxidation kinetic models of three carbon materials studied were analyzed by mechanism-function method. The results indicate that three carbon species adopt different oxidation mechanisms due to their different structures. The oxidation of carbon nanotubes with cylindrical structure follows contracting volume reaction mechanism [R3 mechanism, 1- (1- α)^1/3 = kt], indicating that the oxidation of carbon nanotubes takes place from the ends to the center. For graphite with planar sandwich structure, the oxidation starts at the edges initially and gradually moves toward the center, which corresponds to contracting area phase boundary reaction mechanism [R2 mechanism, 1 - (1 - α)^1/2 = kt]. The oxidation of C60 with spherical structure, however, is complex and apparently cannot be illustrated with a single kinetic model. The values of apparent activation energy obtained by the mechanism-function method are (145 ± 5) kJ·mol^-1 for carbon nanotubes and (193 ± 7) kJ·mol^-1 for graphite, respectively, while the value of apparent activation energy for C60 determined using Kissinger method is 91 kJ·mol^-1。展开更多
The oxidation kinetics and composition of oxide scales on low carbon steel （SPHC） were studied during i- sothermal oxidation. Thermogravimetric analyzer （TGA） was used to simulate isothermal oxidation process of S...The oxidation kinetics and composition of oxide scales on low carbon steel （SPHC） were studied during i- sothermal oxidation. Thermogravimetric analyzer （TGA） was used to simulate isothermal oxidation process of SPHC for 240 min under air condition, and the temperature range was from 500 to 900 ℃. Scanning electron microscope （SEM） was used to observe cross-sectional scale morphology and analyze composition distribution of oxide scales. The morphology of oxide scale was classical three-layer structure. Fe2 03 developed as whiskers at the outermost lay- er, and interlayer was perforated-plate Fe3 04 while innermost layer was pyramidal FeO. From the oxidation curves, the oxidation mass gain per unit area with time was of parabolic relation and oxidation rate slowed down. On the ba- sis of experimental data, the isothermal oxidation kinetics model was derived and oxidation activation energy of SPHC steel was 127. 416 kJ/mol calculated from kinetics data.展开更多
Gold bearing pyrite leaching was conducted in H2SO4-Fe2（SO4）3 system at different reaction temperatures,with different ferric ion concentrations,sulfuric acid concentrations and stirring speeds.The leaching kinetics...Gold bearing pyrite leaching was conducted in H2SO4-Fe2（SO4）3 system at different reaction temperatures,with different ferric ion concentrations,sulfuric acid concentrations and stirring speeds.The leaching kinetics and mechanism were studied.When the temperature ranged between 30-75 °C,the pyrite leaching was mainly controlled by chemical reaction with positive correlation to the ferric ion concentration.The activation energy obtained from Arrhenius empirical formula is 51.39 k J/mol.The EDS and XPS analyses suggest that the oxidation of sulfur within pyrite is through a series of intermediate stages,and eventually is oxidized to sulphate accompanied with the formation of element sulfur.This indicates a thiosulfate oxidation pathway of the gold bearing pyrite oxidation in H2SO4-Fe2（SO4）3 system.展开更多
The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction （SCR） of nitric oxide （NO） with NH3. The kinetics of the SCR reaction in the pre...The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction （SCR） of nitric oxide （NO） with NH3. The kinetics of the SCR reaction in the presence of O2 was studied in this work. The results showed that the observed reaction orders were 0.74-0.99, 0.01-0.13, and 0 for NO, O2 and NH3 at 350-450℃, respectively. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst. The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N2 and H2O. Gaseous O2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process. It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH3.展开更多
p -Xylene liquid phase oxidation at different temperatures of 186-197 ℃ was carried out to investigate the temperature effect. The kinetics model developed in Part(Ⅰ) was used to fit the data.The rate constants obta...p -Xylene liquid phase oxidation at different temperatures of 186-197 ℃ was carried out to investigate the temperature effect. The kinetics model developed in Part(Ⅰ) was used to fit the data.The rate constants obtained can be well represented by the Arrhenius relationship.The obtained activation energy of different reaction steps ranged from 54 kJ·mol -1 to 93 kJ·mol -1 , among them the activation energy of p -toluic acid to 4-carboxybenzaldehyde step was the highest (92.8 kJ·mol -1 ) and that of 4-carboxybenzaldehyde to terephthalic acid step was the second(84.9 kJ·mol -1 ).They are remarkably higher than the values of the other steps (54.94-67.53 kJ·mol -1 ). This fact showed that oxidation of the second methyl group of p -xylene was more sensitive to the temperature variation than the first one.展开更多
基金the National Key Research and Development Program of China(No.2016YFB0301104)Nation Natural Science Foundation of China(No.51771043)Foundation of State Key Laboratory of Baiyunobo Rare Earth researches and Comprehensive Utilization,and Programme of Introducing Talents of Discipline Innovation to Universities 2.0(the 111 Project 2.0 of China,No.BP0719037).
文摘The oxidation behaviors of AZ80,AZ8O-0.32 Y and AZ8O-0.38 Nd(wt.%)alloys were researched at 413℃,420℃,427v and 433℃for up to 6 h in air environment via a high precision analytical balance,a laser confocal microscope,differential scanning calorimeter(DSC)analysis,X-ray diffraction(XRD)analysis,scanning electron microscope(SEM)observation,and X-ray photoelectron spectroscopy(XPS)analysis.The results show that the weight gain and oxidation rate of AZ80 are reduced significantly,the initiation form and propagation of cracks in oxide layer are changed.Compact and protective oxide layer forms on alloy surface with Y or Nd addition.And the activation energies of AZ80,AZ80-0.32Y and AZ8O-0.38Nd alloys calculated via Arrhenius equation are 82.556 kJ/mol,177.148kJ/mol and 136.738 kJ/mol,respectively.
基金This work was financially supported by the National Key Research and Development Program of China(No.2018YFC1900500)Graduate Research and Innovation Foundation of Chongqing,China(No.CYB17002).
文摘The oxidation pathway and kinetics of titania slag powders in air were analyzed using differential scanning calorimetry(DSC)and thermogravimetry(TG).The oxidation pathway of titania slag powder in air was divided into three stages according to their three exothermic peaks and three corresponding mass gain stages indicated by the respective non-isothermal DSC and TG curves.The isothermal oxidation kinetics of high titania slag powders of different sizes were analyzed using the ln-ln analysis method.The results revealed that the entire isothermal oxidation process comprises two stages.The kinetic mechanism of the first stage can be described as f(α) = 1.77(1-α) [-ln (1-α)]^((1.77-1)/1.77),f(α)= 1.97(1-α) [-ln (1-α)]^((1.97-1)/1.97),and f (α) = 1.18(1-α) [-ln (1-α)]^((1.18-1)/1.18).The kinetic mechanism of the second stage for all samples can be described as f (α)=1.5(1-α)^(2/3)[1-(1-α)^(1/3)]^(-1).The activation energies of titania slag powders with different sizes(d_(1)<0.075 mm,0.125 mm<d_(2)<0.150 mm,and 0.425 mm<d_(3)<0.600 mm)for different reaction degrees were calculated.For the given experimental conditions,the rate-controlling step in the first oxidation stage of all the samples is a chemical reaction.The rate-controlling steps of the second oxidation stage are a chemical reaction and internal diffusion(for powders d_(1)<0.075 mm)and internal diffusion(for powders 0.125 mm<d_(2)<0.150 mm and 0.425 mm<d_(3)<0.600 mm).
基金Project(2005BA639C) supported by the National Science and Technology Development of China
文摘The kinetic behavior of leaching copper from low grade copper oxide ore was investigated. The effects of leaching temperature, H2SO4 concentration, particle size of crude ore and agitation rate on the leaching efficiency of copper were also evaluated. And the kinetic equations of the leaching process were obtained. The results show that the leaching process can be described with a reaction model of shrinking core. The reaction can be divided into three stages. The first stage is the dissolution of free copper oxide and copper oxide wrapped by hematite-limonite ore. At this stage, the leaching efficiency is very fast （leaching efficiency is larger than 60%）. The second stage is the leaching of diffiuent copper oxides, whose apparent activation energy is 43.26 kJ/mol. During this process, the chemical reaction is the control step, and the reaction order of H2SO4 is 0.433 84. The third stage is the leaching of copper oxide wrapped by hematite-limonite and silicate ore with apparent activation energy of 16.08 kJ/mol, which belongs to the mixed control.
文摘Clay samples containing 8.15% iron oxides and 27.49% alumina were leached in oxalic acid. Leaching experiments were per-formed in aqueous solutions of oxalic acid of 0.2-2 mol/L at 40-80 C for up to 90 min. The mixed kinetic mechanism, i.e., t/τ=[（1 2X/3） （1 X）2/3 ]＋b[ 1 （1 X）1/3], seemed to be the most appropriate one to fit the kinetic data of leaching iron oxides contained in clay in the aqueous oxalic acid solutions. The Arrhenius activation energy for leaching in the 1.8 mol/L oxalic acid was found to be 41.035 kJ/mol.
基金Supported by the Natural Science Foundation of Zhejiang Province (No. 500105).
文摘The oxidation of carbon nanotubes, C60 and graphite was studied by thermogravimetric (TG) analysis and differential thermal analysis (DTA) technique, and the oxidation kinetic models of three carbon materials studied were analyzed by mechanism-function method. The results indicate that three carbon species adopt different oxidation mechanisms due to their different structures. The oxidation of carbon nanotubes with cylindrical structure follows contracting volume reaction mechanism [R3 mechanism, 1- (1- α)^1/3 = kt], indicating that the oxidation of carbon nanotubes takes place from the ends to the center. For graphite with planar sandwich structure, the oxidation starts at the edges initially and gradually moves toward the center, which corresponds to contracting area phase boundary reaction mechanism [R2 mechanism, 1 - (1 - α)^1/2 = kt]. The oxidation of C60 with spherical structure, however, is complex and apparently cannot be illustrated with a single kinetic model. The values of apparent activation energy obtained by the mechanism-function method are (145 ± 5) kJ·mol^-1 for carbon nanotubes and (193 ± 7) kJ·mol^-1 for graphite, respectively, while the value of apparent activation energy for C60 determined using Kissinger method is 91 kJ·mol^-1。
基金Sponsored by National Natural Science Foundation of China(51204047)National Key Technology Research and Development Program in 12th Five-year Plan of China(2011BAE13B04)The Fundamental Research Funds for the Central Universities of China(N100307006)
文摘The oxidation kinetics and composition of oxide scales on low carbon steel （SPHC） were studied during i- sothermal oxidation. Thermogravimetric analyzer （TGA） was used to simulate isothermal oxidation process of SPHC for 240 min under air condition, and the temperature range was from 500 to 900 ℃. Scanning electron microscope （SEM） was used to observe cross-sectional scale morphology and analyze composition distribution of oxide scales. The morphology of oxide scale was classical three-layer structure. Fe2 03 developed as whiskers at the outermost lay- er, and interlayer was perforated-plate Fe3 04 while innermost layer was pyramidal FeO. From the oxidation curves, the oxidation mass gain per unit area with time was of parabolic relation and oxidation rate slowed down. On the ba- sis of experimental data, the isothermal oxidation kinetics model was derived and oxidation activation energy of SPHC steel was 127. 416 kJ/mol calculated from kinetics data.
基金Project(51474075)supported by the National Natural Science Foundation of China
文摘Gold bearing pyrite leaching was conducted in H2SO4-Fe2（SO4）3 system at different reaction temperatures,with different ferric ion concentrations,sulfuric acid concentrations and stirring speeds.The leaching kinetics and mechanism were studied.When the temperature ranged between 30-75 °C,the pyrite leaching was mainly controlled by chemical reaction with positive correlation to the ferric ion concentration.The activation energy obtained from Arrhenius empirical formula is 51.39 k J/mol.The EDS and XPS analyses suggest that the oxidation of sulfur within pyrite is through a series of intermediate stages,and eventually is oxidized to sulphate accompanied with the formation of element sulfur.This indicates a thiosulfate oxidation pathway of the gold bearing pyrite oxidation in H2SO4-Fe2（SO4）3 system.
基金Project supported by the CCSS of Shanxi Provincial Government of China(No.200032,200516)
文摘The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction （SCR） of nitric oxide （NO） with NH3. The kinetics of the SCR reaction in the presence of O2 was studied in this work. The results showed that the observed reaction orders were 0.74-0.99, 0.01-0.13, and 0 for NO, O2 and NH3 at 350-450℃, respectively. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst. The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N2 and H2O. Gaseous O2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process. It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH3.
文摘p -Xylene liquid phase oxidation at different temperatures of 186-197 ℃ was carried out to investigate the temperature effect. The kinetics model developed in Part(Ⅰ) was used to fit the data.The rate constants obtained can be well represented by the Arrhenius relationship.The obtained activation energy of different reaction steps ranged from 54 kJ·mol -1 to 93 kJ·mol -1 , among them the activation energy of p -toluic acid to 4-carboxybenzaldehyde step was the highest (92.8 kJ·mol -1 ) and that of 4-carboxybenzaldehyde to terephthalic acid step was the second(84.9 kJ·mol -1 ).They are remarkably higher than the values of the other steps (54.94-67.53 kJ·mol -1 ). This fact showed that oxidation of the second methyl group of p -xylene was more sensitive to the temperature variation than the first one.
