Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energ...Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energy was calculated,and the results indicate that the overall reaction involves more than one single step.The reaction with a lower content(<15 wt%)of calcium hydroxide can be divided into two steps,while the reaction with a higher content(>15 wt%)involves another step which denotes the decomposition of newly formed calcium carbonate during roasting.The activation energy increases with increasing amount of calcium hydroxide in the lower range(0-15 wt%).This is due to the resistance of calcium hydroxide to heat and mass transport,However,more calcium can promote the decomposition reaction more effectively and thus reduce the activation energy.Nonlinear fitting was performed by fitting the experimental data to Avrami-Erofeev model to determine the reaction model and pre-exponential factor.The theoretical models were proven to be reliable for kinetic prediction.展开更多
The modern trend of increasing the number of pigs at production sites led to a noticeable surplus of manure. Separation of manure solids provides an avenue of their utility via thermochemical conversion techniques. Th...The modern trend of increasing the number of pigs at production sites led to a noticeable surplus of manure. Separation of manure solids provides an avenue of their utility via thermochemical conversion techniques. Therefore, the goal of this paper was to assess the physical and thermal properties of solid separated swine manure obtained from two different farms, i.e., farrowing, and growing-finishing, and to determine their pyrolysis kinetic parameters. Swine manure solids were dried and milled prior to assessing their properties. Differential and integral isoconversional methods (Friedman, and Flynn-Wall-Ozawa) were used to determine the apparent activation energy as a function of the conversion ratio. Significant differences were observed in the proximate, ultimate composition between both manure types. The higher heating value (HHV) for the manure solids from farrowing, and growing-finishing farms reached 16.6 MJ/kg and 19.4 MJ/kg, respectively. The apparent activation energy computed using Friedman and FWO methods increased with the increase in the degree of conversion. Between 10% and 40% degrees of conversion, the average activation energies, using Friedman method, were103 and 116 kJ/mol for the farrowing and growing-finishing manure solids, respectively. On the other hand, the same activation energies, calculated from FWO method, were 98 and 104 kJ/mol, for solid manure obtained from farrowing and growing-finishing farms, respectively. The findings in this study will assist in the effort to optimize thermochemical conversion processes to accommodate swine waste. This could, in turn, minimize swine production impacts on the surrounding ecologies and provide sustainable energy and biochar streams.展开更多
The Democratic Republic of the Congo holds important reserves of oil shale which is still under geological status.Herein,the characterization and pyrolysis kinetics of typeⅠkerogen-rich oil shale of the western Centr...The Democratic Republic of the Congo holds important reserves of oil shale which is still under geological status.Herein,the characterization and pyrolysis kinetics of typeⅠkerogen-rich oil shale of the western Central Kongo(CK)were investigated.X-ray diffraction,Fourier-transform infrared spectroscopy and thermal analysis(TG/DTA)showed that CK oil shale exhibits a siliceous mineral matrix with a consistent organic matter rich in aliphatic chains.The pyrolysis behavior of kerogen revealed the presence of a single mass loss between 300 and 550°C,estimated at 12.5%and attributed to the oil production stage.Non-isothermal kinetics was performed by determining the activation energy using the iterative isoconversional model-free methods and exhibits a constant value with E=211.5±4.7 kJ mol.1.The most probable kinetic model describing the kerogen pyrolysis mechanism was obtained using the Coats–Redfern and Arrhenius plot methods.The results showed a unique kinetic triplet confirming the nature of kerogen,predominantly typeⅠand reinforcing the previously reported geochemical characteristics of the CK oil shale.Besides,the calculation of thermodynamic parameters(ΔH~*,ΔS~*andΔG~*)corresponding to the pyrolysis of typeⅠkerogen revealed that the process is non-spontaneous,in agreement with DTA experiments.展开更多
A new method of the multiple rates isotemperature is proposed to define the most probable mechanismg(α) of thermal anlaysis; the iterative isoconversional procedure has been employed to estimate apparent activation e...A new method of the multiple rates isotemperature is proposed to define the most probable mechanismg(α) of thermal anlaysis; the iterative isoconversional procedure has been employed to estimate apparent activation energyE; the pre-exponential factorA is obtained on the basis ofE andg(α). By this new method, the thermal analysis kinetics triplet of dehydration of cobalt oxalate dihydrate is determined, apparent activation energyE is 99.84 kJ·mol?1; pre-exponential factorA is 3.427×109–3.872×109 s?1 and the most probable mechanism belongs to nucleation and growth,A m model, the range ofm is from 1.50 to 1.70. Key words multiple rates isotemperature method - isoconversional method - cobalt oxalate dihydrate - accomodation function - differential scanning calorimetry (DSC) CLC number O 636.1 Foundation item: Supported by the Key Foundation of the Science and Technology Committee of Hubei Province (2001ABA009)Biography: Li Li-qing (1977-), female, Master candidate, research direction: material synthesize and thermal analysis kinetics.展开更多
The nitrate complexes of cerium, praseodymium and neodymium with 1,10-phenanthroline (phen) of general formula [Ln(phen)2(NO3)2(H2O)2]·NO3 (where, Ln=Ce, Pr and Nd) were prepared and characterized by X-...The nitrate complexes of cerium, praseodymium and neodymium with 1,10-phenanthroline (phen) of general formula [Ln(phen)2(NO3)2(H2O)2]·NO3 (where, Ln=Ce, Pr and Nd) were prepared and characterized by X-ray crystallography. Thermolysis of these complexes was investigated by simultaneous thermogravimetry (TG) and differential thermal analysis (DTA). Isothermal TG was taken to evaluate the kinetic parameters using model fitting as well as model free isoconversional methods. The thermolytic pathways were also suggested, which involves decomposition followed by ignition. All the three complexes had coordination number ten and showed multistep decompositions. In order to evaluate the response of rapid heating, ignition delay (Di) measurements were undertaken. The activation energies for ignition were found to decrease in the order: Nd〉Pr〉Ce.展开更多
Ceria nano discs were synthesized by the stepwise thermal decomposition strategy of the oxalate precursor. A series of Ce(1-x)CuxO2(x = 0, 0.02, 0.1, 0.2 and 0.3) nano sized oxide systems were prepared through the...Ceria nano discs were synthesized by the stepwise thermal decomposition strategy of the oxalate precursor. A series of Ce(1-x)CuxO2(x = 0, 0.02, 0.1, 0.2 and 0.3) nano sized oxide systems were prepared through thermal decomposition route. Kinetic characterization of formation of solid solution was made by isoconversional strategy under non-isothermal condition. Introduction of various reactant molar ratios of Cu2+:Ce4+ has a pivotal role in the creation of new oxygen vacancies, decomposition strategy,particle size and shape. Cu2+ doping(x = 0.02 and 0.1) damages the disc shaped morphology of ceria.Homogeneous distribution of Cu2+ on the oxalate precursor has a significant role in the catalyzing activity for the destruction of oxalate bond to oxide. 2 mol% doped Cu2+ promotes breaking of oxalate bonds in nitrogen atmosphere. In vitro cell viability assay illustrates enhanced toxicity to cancer cells with 10 mol% Cu2+ doped ceria.展开更多
基金Project supported by the National Basic Research Program(973 Program,2012CBA01205)。
文摘Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energy was calculated,and the results indicate that the overall reaction involves more than one single step.The reaction with a lower content(<15 wt%)of calcium hydroxide can be divided into two steps,while the reaction with a higher content(>15 wt%)involves another step which denotes the decomposition of newly formed calcium carbonate during roasting.The activation energy increases with increasing amount of calcium hydroxide in the lower range(0-15 wt%).This is due to the resistance of calcium hydroxide to heat and mass transport,However,more calcium can promote the decomposition reaction more effectively and thus reduce the activation energy.Nonlinear fitting was performed by fitting the experimental data to Avrami-Erofeev model to determine the reaction model and pre-exponential factor.The theoretical models were proven to be reliable for kinetic prediction.
文摘The modern trend of increasing the number of pigs at production sites led to a noticeable surplus of manure. Separation of manure solids provides an avenue of their utility via thermochemical conversion techniques. Therefore, the goal of this paper was to assess the physical and thermal properties of solid separated swine manure obtained from two different farms, i.e., farrowing, and growing-finishing, and to determine their pyrolysis kinetic parameters. Swine manure solids were dried and milled prior to assessing their properties. Differential and integral isoconversional methods (Friedman, and Flynn-Wall-Ozawa) were used to determine the apparent activation energy as a function of the conversion ratio. Significant differences were observed in the proximate, ultimate composition between both manure types. The higher heating value (HHV) for the manure solids from farrowing, and growing-finishing farms reached 16.6 MJ/kg and 19.4 MJ/kg, respectively. The apparent activation energy computed using Friedman and FWO methods increased with the increase in the degree of conversion. Between 10% and 40% degrees of conversion, the average activation energies, using Friedman method, were103 and 116 kJ/mol for the farrowing and growing-finishing manure solids, respectively. On the other hand, the same activation energies, calculated from FWO method, were 98 and 104 kJ/mol, for solid manure obtained from farrowing and growing-finishing farms, respectively. The findings in this study will assist in the effort to optimize thermochemical conversion processes to accommodate swine waste. This could, in turn, minimize swine production impacts on the surrounding ecologies and provide sustainable energy and biochar streams.
基金financially supported by University of Mohammed V-Morocco under the Project No.SCH 04/09 and HassanⅡAcademy of Science and Technology,Morocco.
文摘The Democratic Republic of the Congo holds important reserves of oil shale which is still under geological status.Herein,the characterization and pyrolysis kinetics of typeⅠkerogen-rich oil shale of the western Central Kongo(CK)were investigated.X-ray diffraction,Fourier-transform infrared spectroscopy and thermal analysis(TG/DTA)showed that CK oil shale exhibits a siliceous mineral matrix with a consistent organic matter rich in aliphatic chains.The pyrolysis behavior of kerogen revealed the presence of a single mass loss between 300 and 550°C,estimated at 12.5%and attributed to the oil production stage.Non-isothermal kinetics was performed by determining the activation energy using the iterative isoconversional model-free methods and exhibits a constant value with E=211.5±4.7 kJ mol.1.The most probable kinetic model describing the kerogen pyrolysis mechanism was obtained using the Coats–Redfern and Arrhenius plot methods.The results showed a unique kinetic triplet confirming the nature of kerogen,predominantly typeⅠand reinforcing the previously reported geochemical characteristics of the CK oil shale.Besides,the calculation of thermodynamic parameters(ΔH~*,ΔS~*andΔG~*)corresponding to the pyrolysis of typeⅠkerogen revealed that the process is non-spontaneous,in agreement with DTA experiments.
文摘A new method of the multiple rates isotemperature is proposed to define the most probable mechanismg(α) of thermal anlaysis; the iterative isoconversional procedure has been employed to estimate apparent activation energyE; the pre-exponential factorA is obtained on the basis ofE andg(α). By this new method, the thermal analysis kinetics triplet of dehydration of cobalt oxalate dihydrate is determined, apparent activation energyE is 99.84 kJ·mol?1; pre-exponential factorA is 3.427×109–3.872×109 s?1 and the most probable mechanism belongs to nucleation and growth,A m model, the range ofm is from 1.50 to 1.70. Key words multiple rates isotemperature method - isoconversional method - cobalt oxalate dihydrate - accomodation function - differential scanning calorimetry (DSC) CLC number O 636.1 Foundation item: Supported by the Key Foundation of the Science and Technology Committee of Hubei Province (2001ABA009)Biography: Li Li-qing (1977-), female, Master candidate, research direction: material synthesize and thermal analysis kinetics.
文摘The nitrate complexes of cerium, praseodymium and neodymium with 1,10-phenanthroline (phen) of general formula [Ln(phen)2(NO3)2(H2O)2]·NO3 (where, Ln=Ce, Pr and Nd) were prepared and characterized by X-ray crystallography. Thermolysis of these complexes was investigated by simultaneous thermogravimetry (TG) and differential thermal analysis (DTA). Isothermal TG was taken to evaluate the kinetic parameters using model fitting as well as model free isoconversional methods. The thermolytic pathways were also suggested, which involves decomposition followed by ignition. All the three complexes had coordination number ten and showed multistep decompositions. In order to evaluate the response of rapid heating, ignition delay (Di) measurements were undertaken. The activation energies for ignition were found to decrease in the order: Nd〉Pr〉Ce.
文摘Ceria nano discs were synthesized by the stepwise thermal decomposition strategy of the oxalate precursor. A series of Ce(1-x)CuxO2(x = 0, 0.02, 0.1, 0.2 and 0.3) nano sized oxide systems were prepared through thermal decomposition route. Kinetic characterization of formation of solid solution was made by isoconversional strategy under non-isothermal condition. Introduction of various reactant molar ratios of Cu2+:Ce4+ has a pivotal role in the creation of new oxygen vacancies, decomposition strategy,particle size and shape. Cu2+ doping(x = 0.02 and 0.1) damages the disc shaped morphology of ceria.Homogeneous distribution of Cu2+ on the oxalate precursor has a significant role in the catalyzing activity for the destruction of oxalate bond to oxide. 2 mol% doped Cu2+ promotes breaking of oxalate bonds in nitrogen atmosphere. In vitro cell viability assay illustrates enhanced toxicity to cancer cells with 10 mol% Cu2+ doped ceria.