The oxygen adsorption/desorption properties of YBaCo4O7 at high temperature were investigated by thermogravimetry(TG) method,in which two types of oxygen adsorption were combined.The first type adsorbed oxygen at abou...The oxygen adsorption/desorption properties of YBaCo4O7 at high temperature were investigated by thermogravimetry(TG) method,in which two types of oxygen adsorption were combined.The first type adsorbed oxygen at about 700 °C and released the adsorbed oxygen at 880 °C.After the first type oxygen desorption,even the temperature and oxygen flow were kept the same,a second type oxygen adsorption at about 880 °C occurred and the adsorbed oxygen were released at above 980 °C.The combination of these two types of...展开更多
Five coal char samples were burnt in thermobalance with ramp heating rate of 30 K/min. The pore structure of these char samples was studied through mercury intrusion method. Combined with the kinetic theory of gases, ...Five coal char samples were burnt in thermobalance with ramp heating rate of 30 K/min. The pore structure of these char samples was studied through mercury intrusion method. Combined with the kinetic theory of gases, the data of surface area was used in fitting the results. As a result, the kinetic triplet was given. The analysis showed that five char samples share almost the same intrinsic activation energy of the overall reaction. The phenomenological implication of the derived combustion rate equation was given.展开更多
Due to the existence of poly-hydroxyl structures,the temperature may have an effect on the thermal stability of oleuropein for its applications.In the current study,the thermal decomposition process and kinetics behav...Due to the existence of poly-hydroxyl structures,the temperature may have an effect on the thermal stability of oleuropein for its applications.In the current study,the thermal decomposition process and kinetics behavior of oleuropein from the olive resource were researched by thermogravimetric theoretical analysis methods and non-isothermal kinetics simulation.The results of thermogravimetry analysis showed the whole thermal decomposi-tion process of oleuropein involved two stages,with 21.22%of residue.It was also revealed that high heating rates of more than 20 K min^(-1) led to significant thermal hysteresis and inhibited the whole thermal decomposition behavior of oleuropein.Moreover,an investigation of the thermal decomposition kinetics indicated that the non-isothermal decomposition behavior followed a D3 model during thefirst stage(three-dimensional diffusion,Jander equation)and a D1 model in the second stage(one-dimensional diffusion).For thefirst and second ther-mal decomposition stages,the Kissinger,Friedman,Flynn-Wall-Ozawa,and Coats–Redfern four methods were applied to determine the activation energy(E=143.72 and 247.01 kJ mol^(-1))and Arrhenius preexponential factor(ln A=26.34 and 42.45 min^(-1)),respectively.Therefore,the study will provide good theoretical guidance for ther-mal stability and thermal transformation application of oleuropein.It will be suitable for low-temperature appli-cations in the cosmetic,food supplement and pharmaceutical industries.展开更多
Replacing solid carbon with hydrogen gas in ferromanganese production presents a forward-thinking,sustainable solution to re-ducing the ferro-alloy industry’s carbon emissions.The HAlMan process,a groundbreaking and ...Replacing solid carbon with hydrogen gas in ferromanganese production presents a forward-thinking,sustainable solution to re-ducing the ferro-alloy industry’s carbon emissions.The HAlMan process,a groundbreaking and eco-friendly method,has been meticu-lously researched and scaled up from laboratory experiments to pilot tests,aiming to drastically cut CO_(2) emissions associated with ferro-manganese production.This innovative process could potentially reduce CO_(2) emissions by about 1.5 tonnes for every tonne of ferroman-ganese produced.In this study,a lab-scale vertical thermogravimetric furnace was used to carry out the pre-reduction of Nchwaning man-ganese ore,where direct reduction occurred with H_(2) gas under controlled isothermal conditions at 700,800,and 900℃.The results indic-ated that higher pre-reduction temperatures(800 and 900℃)effectively converted Fe_(2)O_(3) to metallic iron and Mn_(2)O_(3) to MnO.By continu-ously monitoring the mass changes during the reduction,both the rate and extent of reduction were assessed.A second-order reaction model was applied to validate the experimental outcomes of H_(2) reduction at various temperatures,showing apparent activation energies of 29.79 kJ/mol for dried ore and 61.71 kJ/mol for pre-calcined ore.The reduction kinetics displayed a strong dependence on temperature,with higher temperatures leading to quicker and more complete reductions.The kinetics analysis suggested that the chemical reaction at the gas-solid interface between hydrogen and the manganese ore is likely the rate-limiting step in this process.展开更多
Chrome shavings(CS),a kind of solid wastes discharged from tanneries,always pose serious environmental problems due to the presence of chromium.In this work,kinetic study of the pyrolysis of CS was investigated using ...Chrome shavings(CS),a kind of solid wastes discharged from tanneries,always pose serious environmental problems due to the presence of chromium.In this work,kinetic study of the pyrolysis of CS was investigated using a thermogravimetric analyzer in nitrogen atmosphere.The results obtained from the thermogravimetric analysis indicated that there are three stages in the temperature range 25 to 600℃.The second stage is the main weight loss stage and it could be mainly attributed to the pyrolysis of collagenous materials.Iso-conversional and generalized master-plots method were first employed to estimate the activation energy value and possible reaction mechanism of CS pyrolysis.The results showed that the pyrolysis process could not be described accurately by single-step reaction due to the heterogeneous nature of CS.Afterwards,the thermogravimetric kinetic of CS pyrolysis was studied using combined kinetic analysis.It was found that three-parallel-reaction model allowed better fitting relevance for CS pyrolysis.This information was important for simulating and predicting the pyrolysis behaviors of CS.展开更多
Refractories have unique capabilities such as sustaining their shape and properties at extreme conditions such as the combination of high temperatures and thermal shock,contact with molten metals and slags and in some...Refractories have unique capabilities such as sustaining their shape and properties at extreme conditions such as the combination of high temperatures and thermal shock,contact with molten metals and slags and in some circumstances resistance to erosion from abrasive particles.Given the large processing output of the heavy industries such as the cement and steel ones which both require high temperature processes,the refractories structures span various meters and weight of several tons.As the water removal stage of hydraulic bonded castables in industrial sites takes hours(10-60 h)due to the risk of explosive spalling,efforts to mitigate it are commonly studied.This has provided theoretical understanding of the general aspects of drying and important tools,such as the thermogravimetry analysis(TGA),for the design of refractory compositions with higher explosive spalling resistance.However,the optimization of this process is still far from the industrial reality especially because the actual linings that require the drying are orders of magnitude larger than the samples considered in the laboratory tests.Therefore,this study proposed the analysis of the sample volume effect on the water removal dynamics through TGA of high alumina castables with calcium aluminate cement.Conventionalφ5 cm×5 cm cylindrical samples were assessed in a laboratory scale equipment whereas macro TGA were carried out considering 20 cm×20 cm×20 cm and 30 cm×30 cm×30 cm cubic samples.Additionally,the effect of polymeric fibers was also considered.It was found out that the different thermal gradients within the macro TGA samples resulted in an inflection on the sample’s heating rate and that the mass loss was affected by the volume considered,especially for the composition without additives.These findings highlight the requirement of carefully taking into consideration the different dimensional sizes and thermal gradients in the samples when analyzing and interpreting the laboratory studies,and especially when trying to extrapolate such results to the industrial reality.展开更多
Despite the fact that a few countries in the Mediterranean and the Middle East have limited crude oil reserves, they have abundant biomass feedstocks. For instance, Jordan relies heavily on the importation of natural ...Despite the fact that a few countries in the Mediterranean and the Middle East have limited crude oil reserves, they have abundant biomass feedstocks. For instance, Jordan relies heavily on the importation of natural gas and crude oil for its energy needs;but, by applying thermochemical conversion techniques, leftover olive oil can be used to replace these energy sources. Understanding the chemical, physical, and thermal characteristics of raw materials is essential to obtaining the most out of these conversion processes. Thermogravimetric analysis was used in this study to examine the thermal behavior of olive-solid residue (kernel) at three different heating rates (5, 20 and 40 C/min) in nitrogen and oxygen atmospheres. The initial degradation temperature, the residual weight at 500 and 700˚C and the thermal degradation rate during the devolatilization stage (below 400˚C) were all determined. It was found that in N<sub>2</sub> and O<sub>2</sub> atmospheres, both the initial degradation temperature and the degradation rate increase with increasing heating rates. As heating rates increase in the N<sub>2</sub> atmosphere, the residual weight at 500 or 700˚C decreases slightly, but at low heating rates compared to high heating rates in the O<sub>2</sub> atmosphere, it decreases significantly. This suggests that a longer lignin oxidation process is better than a shorter one. Coats and Redfern approach was used to identify the mechanism and activation energy for the devolatilization stage of pyrolysis and oxidation reactions. The process mechanism analysis revealed that the model of first-order and second-order reactions may adequately describe the mechanism of heat degradation of the devolatilization step of olive-solid waste for pyrolysis and oxidation processes, respectively.展开更多
In order to evaluate the spontaneous combustion hazard of sulfide concentrates in storage, three different kinds of sulfide concentrates （sulfur-rich sulfide concentrate, iron sulfide concentrate and copper sulfide c...In order to evaluate the spontaneous combustion hazard of sulfide concentrates in storage, three different kinds of sulfide concentrates （sulfur-rich sulfide concentrate, iron sulfide concentrate and copper sulfide concentrate） were obtained from a storage yard in Dongguashan Copper Mine, China. The reaction processes at different heating rates of 5, 10, 15, 20, and 25 ℃/min in air flow from ambient temperature to 1 000 ℃ were studied by TG-DTG-DSC analysis. By the peak temperatures of DTG curves, the whole reaction process for each sample was divided into different stages, and the corresponding apparent activation energies were calculated by the Ozawa-Flynn-Wall method. It is found that the reaction process of each sample is considerably complex; the apparent activation energy values change from 36 to 160 kJ/mol in different temperature ranges; sulfur-rich sulfide and iron sulfide concentrates have lower apparent activation energy than copper sulfide concentrate below 150 ℃; so they are more inclined to cause spontaneous combustion at ambient temperature.展开更多
Bi0.9La0.1Fe0.95Mn0.05O3 （BLFMO） ferroelectric thin films were fabricated on Pt/Ti/SiO2/Si/ substrates by the sol-gel process at different pyrolysis temperatures. The mass loss of BLFMO powder was investigated by th...Bi0.9La0.1Fe0.95Mn0.05O3 （BLFMO） ferroelectric thin films were fabricated on Pt/Ti/SiO2/Si/ substrates by the sol-gel process at different pyrolysis temperatures. The mass loss of BLFMO powder was investigated by thermo gravimetry analyser （TGA）, and the polycrystalline structure and smooth surface of BLFMO thin films were characterized by X-ray diffraction （XRD） and atomic force microscopy （AFM）, respectively. The remnant polarization （Pr） of the BLFMO films pyrolyzed at 420 ℃ is 21.2 μC/cm2 at the coercive field （Ec） of 99 kV/cm and the leakage current density is 7.1×10-3 A/cm2, which indicates that the BLFMO thin films display relatively good ferroelectric property at this temperature.展开更多
CO2 gasification of Fuijian high-metamorphous anthracite with black liquor （BL） and/or mixture of BL and calcium stuff （BL＋Ca） as catalyst was studied by using a thermogravimetry under 750-950℃ at ambient pressu...CO2 gasification of Fuijian high-metamorphous anthracite with black liquor （BL） and/or mixture of BL and calcium stuff （BL＋Ca） as catalyst was studied by using a thermogravimetry under 750-950℃ at ambient pressure. When the coal was impregnated with an appropriate quantity of Ca and BL mixture, the catalytic activity of CO2 gasification was enhanced obviously. With a loading of 8%Na-BL＋2%Ca, the carbon conversion of three coal samples tested reaches up to 92.9%-99.3% at 950℃ within 30min. The continuous formation of alkali surface compounds such as （[-COM], [-CO2M]） and the presence of exchanged Ca, such as calcium phenolate and calcium carboxylates （COO）2Ca, contribute to the increase in catalytic efficiency, and using BL＋Ca is more efficient than that adding BL only, The homogeneous model and shrinking-core model were applied to correlate the data of conversion with time and to estimate the reaction rate constants under different temperature. The corresponding reaction activation energy （Ea） and pre-exponential factor of three anthracites were estimated. It is found that Ea is in the range from 73.6 to 121.4kJ·mol^-1 in the case of BL＋Ca, and 74.3 to 104.2kJ·mol^-1 when only BL was used as the catalyst, both of which are much less than that from 143.5 to 181.4kJ·mol^-1 if no catalyst used. It is clearly demonstrated that both of BL＋Ca mixture and BL could be the source of cheap and effective catalyst for coal gasification.展开更多
The catalytic effects of single and mixed catalysts, i.e. single 3%Ca and 5%Na-BL（black liquor） catalysts and mixed 3%Ca＋5%Na-BL catalyst, on carbon conversion, gasification reaction rate constant and activation en...The catalytic effects of single and mixed catalysts, i.e. single 3%Ca and 5%Na-BL（black liquor） catalysts and mixed 3%Ca＋5%Na-BL catalyst, on carbon conversion, gasification reaction rate constant and activation energy, relative amount of harmful pollutant like sulphur containing gases have been investigated by thermogravimetry in steam gasification under temperature 750℃ to 950℃ at ambient pressure for three high-metarnorphous anthracites （Longyan, Fenghai and Youxia coals in Fujian Province）. The mixed catalyst of 3%Ca＋5%Na-BL increases greatly the carbon conversion and gasification rate constant by accelerating the gasification reaction C＋H2O→CO＋H2 due to presence of alkali surfacecompounds [COM], [CO2M] and exchanged calcium phenolate and calcium carboxylate （-COO）2. By adding CaCO3 into BL catalyst in gasification, in addition to improving the catalyst function and enhancing the carbon conversion, the effective desulphurization is also achieved, but the better operating temperature should be below 900℃. The homogenous and shrinking core models can be successfully employed to correlate the relations between the conversion and the gasification .time .and to estimate the reaction rate constant, The reaction acUvaUon energy and pre-exponential factor are estimated and the activation energy for mixed catalyst is in a range of 98.72-166.92 kJ·mol^-1, much less than 177.50-196.46 kJ·mol^-1 for non-catalytic steam gasification for three experimental coals.展开更多
The kinetics of isothermal reduction of the carbon bearing pellets, which were mainly composed of Bayanobo complex iron ore and pulverized coal, was investigated by thermogravimetry at the temperature of 1 273-1 673 K...The kinetics of isothermal reduction of the carbon bearing pellets, which were mainly composed of Bayanobo complex iron ore and pulverized coal, was investigated by thermogravimetry at the temperature of 1 273-1 673 K. The effects of xC/xO and the atmospheres on the extent of reduction also were investigated. The results indicate that the fractional reaction increased proportionally with temperature increasing and heating temperature is the significant influence factor to the reaction of carbon bearing pellets. The optimum xC/xO is 1.2 and the effect of atmosphere on the reduction of iron oxides is almost negligible. The results can be interpreted that the reaction was initially controlled by a mixed controlled mechanism of carbon gasification and interface chemical reaction, and in the later stage, interface chemical reaction became the rate-controlling step. Apparent activation energy values of reduction at different levels of fractional reaction were calculated. Before F （fraction of reaction）=0.5, the apparent activation energy ranges from 66.39 to 75.64 kJ/mol, while after F=0.5, the apparent activation energy is 80.98 to 85.37 kJ/mol.展开更多
A novel potential tridentate Schiff base was prepared by condensing equimolar quantities of 2-hydroxyacetophenone and 2-aminopyrimidine in methanol. This ligand was versatile in forming a series of complexes with lant...A novel potential tridentate Schiff base was prepared by condensing equimolar quantities of 2-hydroxyacetophenone and 2-aminopyrimidine in methanol. This ligand was versatile in forming a series of complexes with lanthanide ions such as La（III）, Pr（III）, Nd（III）, Sm（III）, Gd（III）, Dy（III） and Yb（III）. The ligand and the metal complexes were characterized through elemental analysis, molar conductance, UV-Visible, IR, 1H NMR, and mass spectral studies. The spectral studies indicated that the ligand was coordinated to the metal ion in neutral tridentate fashion through the azomethine nitrogen, one of the nitrogen atoms in the pyrimidine ring and the phenolic oxygen without deprotonation. Thermal decomposition and luminescence property of lanthanum（III） complex were also examined. The X-ray diffraction patterns showed the crystalline nature of the ligand and its lanthanum（III） complex. The DNA cleavage studies of the ligand and the metal complexes were carried out and it was observed that the lanthanum（III） and neo-dymium（III） complexes cleaved the pUC19 DNA effectively. The ligand and the metal complexes were screened for their antibacte-rial activities. The metal complexes were found to be more potent bactericides than the ligand.展开更多
High-phosphorus iron ore resource is considered a refractory iron ore because of its high-phosphorus content and complex ore phase structure. Therefore, the development of innovative technology to realize the efficien...High-phosphorus iron ore resource is considered a refractory iron ore because of its high-phosphorus content and complex ore phase structure. Therefore, the development of innovative technology to realize the efficient utilization of high-phosphorus iron ore resources is of theoretical and practical significance. Thus, a method for phosphorus removal by gasification in the hydrogen-rich sintering process was proposed. In this study, the reduction mechanism of phosphorus in hydrogen-rich sintering, as well as the reduction kinetics of apatite based on the non-isothermal kinetic method, was investigated. Results showed that, by increasing the reduction time from 20 to 60 min, the dephosphorization rate increased from 10.93%to 29.51%. With apatite reduction, the metal iron accumulates, and part of the reduced phosphorus gas is absorbed by the metal iron to form stable iron-phosphorus compounds, resulting in a significant reduction of the dephosphorization rate. Apatite reduction is mainly concentrated in the sintering and burning zones, and the reduced phosphorus gas moves downward along with flue gas under suction pressure and is condensed and adsorbed partly by the sintering bed when passing through the drying zone and over the wet zone. As a result, the dephosphorization rate is considerably reduced. Based on the Ozawa formula of the iso-conversion rate, the activation energy of apatite reduction is 80.42 kJ/mol. The mechanism function of apatite reduction is determined by a differential method (i.e., the Freeman-Carroll method) and an integral method (i.e., the Coats-Redfern method). The differential form of the equation is f(α)=2(1-α)^(1/2), and the integral form of the equation is G(α)=1-(1-α)^(1/2).展开更多
The flammability characterization and thermal composition of polymers flame retarded by decabromodiphenylethane (DBDPE) and antimony trioxide (Sb2O3) were studied by cone calorimeter and thermogravimetry (TG). The res...The flammability characterization and thermal composition of polymers flame retarded by decabromodiphenylethane (DBDPE) and antimony trioxide (Sb2O3) were studied by cone calorimeter and thermogravimetry (TG). The results show that ABS/DBDPE/Sb2O3 has the similar flammability parameters and thermal composition curves to ABS/DBDPO/Sb2O3. It suggests that DBDPE/Sb2O3 has the similar flame retardant behavior to DBDPO/Sb2O3. The heat release rate (HRR) and the effect heat combustion (EHC) curves of polymers flame retarded by DBDPE/Sb2O3 all decrease, but the mass loss rate (MLR) curve slightly increase. It shows that the decrease of HRR is not due to the increase of char formation ratio but the generation of incombustible gases. The major flame retardant mechanism of DBDPE/Sb2O3 is gas phase flame retardant mechanism. Increasing content of Sb2O3 in DBDPE/Sb2O3 can improve the flame retardant property and thermal stability of acrylonitrile butadiene styrene. Sb2O3 has a good synergistic effect with DBDPE.展开更多
The oxygen adsorption/desorption properties of double perovskite structure oxides PrBaCo2O5＋δ,GdBaCo2O5＋δ,and YBaCo2O5＋δ were investigated by the thermogravimetry（TG）method in the temperature range of 400~900 ...The oxygen adsorption/desorption properties of double perovskite structure oxides PrBaCo2O5＋δ,GdBaCo2O5＋δ,and YBaCo2O5＋δ were investigated by the thermogravimetry（TG）method in the temperature range of 400~900 ℃.The calculated oxygen adsorption/desorption surface reaction rate constants ka and kd of these double perovskite structure oxides were larger than the commonly used cubic perovskite oxides,such as Ba0.95Ca0.05Co0.8Fe0.2O3-δ and Ba0.5Sr0.5Co0.8Fe0.2O3-δ,whereas,the oxygen permeation flux was comparable to that of the latter,which was attributed to the smaller difference of oxygen vacancy in oxygen and nitrogen atmosphere（Δδ/Vmol）in these double perovskite structure oxides.The large oxygen adsorption/desorption rate constants of GdBaCo2O5＋δ and PrBaCo2O5＋δ made them nice catalyst coating materials,on other membrane surfaces,to improve the oxygen permeability.展开更多
Phase-field modeling approach has been used to study the oxidation behavior of pure Ni when considering heat conduction. In this calculation, the dependence of the coefficient of the Cahn–Hilliard equation Lc on the ...Phase-field modeling approach has been used to study the oxidation behavior of pure Ni when considering heat conduction. In this calculation, the dependence of the coefficient of the Cahn–Hilliard equation Lc on the temperature T was considered. To this end, high-temperature oxidation experiments and phase-field modeling for pure Ni were performed in air under atmospheric pressure at 600,700, and 800？C. The oxidation rate was measured by thermogravimetry and Lc at these temperatures was determined via interactive algorithm. With the Lc-T relationship constructed, oxidation behavior of Ni when considering heat conduction was investigated. The influence of temperature boundaries on the oxidation degree, oxide film thickness, and specific weight gain were discussed. The phase-field modeling approach proposed in this study will give some highlights of the oxidation resistance analysis and cooling measures design of thermal protection materials.展开更多
Three new transition metal complexes have been synthesized with a Schiff base, 3-（2-hydroxy-5-chlorophenylimino）-1,3- diphenylpropen-l-one. In all complexes Schiff base is completely deprotonated and coordinated to ...Three new transition metal complexes have been synthesized with a Schiff base, 3-（2-hydroxy-5-chlorophenylimino）-1,3- diphenylpropen-l-one. In all complexes Schiff base is completely deprotonated and coordinated to metal as tridentate ligand via phenolic and enolic oxygens and imine nitrogen. Thermal decomposition of the complexes has been studied by thermogravimetry. The in vitro antibacterial activity of Schiff bases and their complexes has been evaluated and compared with the standard drugs.展开更多
Five Shenfu char samples were prepared from Shenfu raw coal at different temperatures （950, 1100, 1200, 1300 and 1400℃） using a muffle furnace. Demineralization of the char samples was performed by treating them wi...Five Shenfu char samples were prepared from Shenfu raw coal at different temperatures （950, 1100, 1200, 1300 and 1400℃） using a muffle furnace. Demineralization of the char samples was performed by treating them with 10% nitric acid for 10 min in a CEM Discover microwave reactor. The gasification of the chars, and corresponding demineralized chars, in a carbon dioxide （CO2） atmosphere was conducted in a Netzsch STA 409Cl31F tempera- ture-programmed thermogravimetry apparatus. The effects of charring temperature and demineralization on the gasification reactivity of chars were systematically investigated. The results show that a char formed at a lower temperature is more reactive except for demineralized char formed at 1100℃, which is less reactive than char formed at 1200℃. Demineralization decreases the char reactivities toward gasification with CO2 to a small extent.展开更多
基金supported by Science and Technology Foundation of Henan Province,China (092102210263)Natural Science Foundation of Department of Education of Henan Province,China (2009B430003)
文摘The oxygen adsorption/desorption properties of YBaCo4O7 at high temperature were investigated by thermogravimetry(TG) method,in which two types of oxygen adsorption were combined.The first type adsorbed oxygen at about 700 °C and released the adsorbed oxygen at 880 °C.After the first type oxygen desorption,even the temperature and oxygen flow were kept the same,a second type oxygen adsorption at about 880 °C occurred and the adsorbed oxygen were released at above 980 °C.The combination of these two types of...
基金The work was subsidized by the Special Funds for Major State Basic Research Projects(973).project number G1999022205.
文摘Five coal char samples were burnt in thermobalance with ramp heating rate of 30 K/min. The pore structure of these char samples was studied through mercury intrusion method. Combined with the kinetic theory of gases, the data of surface area was used in fitting the results. As a result, the kinetic triplet was given. The analysis showed that five char samples share almost the same intrinsic activation energy of the overall reaction. The phenomenological implication of the derived combustion rate equation was given.
基金This work was funded by Guangdong Basic and Applied Basic Research Foundation(No.2019A1515111159)Characteristic Innovative Projects for Education Department of Guangdong Province 2021 Year(No.2021KTSCX302).
文摘Due to the existence of poly-hydroxyl structures,the temperature may have an effect on the thermal stability of oleuropein for its applications.In the current study,the thermal decomposition process and kinetics behavior of oleuropein from the olive resource were researched by thermogravimetric theoretical analysis methods and non-isothermal kinetics simulation.The results of thermogravimetry analysis showed the whole thermal decomposi-tion process of oleuropein involved two stages,with 21.22%of residue.It was also revealed that high heating rates of more than 20 K min^(-1) led to significant thermal hysteresis and inhibited the whole thermal decomposition behavior of oleuropein.Moreover,an investigation of the thermal decomposition kinetics indicated that the non-isothermal decomposition behavior followed a D3 model during thefirst stage(three-dimensional diffusion,Jander equation)and a D1 model in the second stage(one-dimensional diffusion).For thefirst and second ther-mal decomposition stages,the Kissinger,Friedman,Flynn-Wall-Ozawa,and Coats–Redfern four methods were applied to determine the activation energy(E=143.72 and 247.01 kJ mol^(-1))and Arrhenius preexponential factor(ln A=26.34 and 42.45 min^(-1)),respectively.Therefore,the study will provide good theoretical guidance for ther-mal stability and thermal transformation application of oleuropein.It will be suitable for low-temperature appli-cations in the cosmetic,food supplement and pharmaceutical industries.
基金the financial support from European Union’s Horizon Europe program HAlMan project (No. 101091936)
文摘Replacing solid carbon with hydrogen gas in ferromanganese production presents a forward-thinking,sustainable solution to re-ducing the ferro-alloy industry’s carbon emissions.The HAlMan process,a groundbreaking and eco-friendly method,has been meticu-lously researched and scaled up from laboratory experiments to pilot tests,aiming to drastically cut CO_(2) emissions associated with ferro-manganese production.This innovative process could potentially reduce CO_(2) emissions by about 1.5 tonnes for every tonne of ferroman-ganese produced.In this study,a lab-scale vertical thermogravimetric furnace was used to carry out the pre-reduction of Nchwaning man-ganese ore,where direct reduction occurred with H_(2) gas under controlled isothermal conditions at 700,800,and 900℃.The results indic-ated that higher pre-reduction temperatures(800 and 900℃)effectively converted Fe_(2)O_(3) to metallic iron and Mn_(2)O_(3) to MnO.By continu-ously monitoring the mass changes during the reduction,both the rate and extent of reduction were assessed.A second-order reaction model was applied to validate the experimental outcomes of H_(2) reduction at various temperatures,showing apparent activation energies of 29.79 kJ/mol for dried ore and 61.71 kJ/mol for pre-calcined ore.The reduction kinetics displayed a strong dependence on temperature,with higher temperatures leading to quicker and more complete reductions.The kinetics analysis suggested that the chemical reaction at the gas-solid interface between hydrogen and the manganese ore is likely the rate-limiting step in this process.
基金the Key Scientific Research Projects of Henan Province,China[grant number 21A430034]National Key R&D Program of China[grant number 2017YFB0308500].
文摘Chrome shavings(CS),a kind of solid wastes discharged from tanneries,always pose serious environmental problems due to the presence of chromium.In this work,kinetic study of the pyrolysis of CS was investigated using a thermogravimetric analyzer in nitrogen atmosphere.The results obtained from the thermogravimetric analysis indicated that there are three stages in the temperature range 25 to 600℃.The second stage is the main weight loss stage and it could be mainly attributed to the pyrolysis of collagenous materials.Iso-conversional and generalized master-plots method were first employed to estimate the activation energy value and possible reaction mechanism of CS pyrolysis.The results showed that the pyrolysis process could not be described accurately by single-step reaction due to the heterogeneous nature of CS.Afterwards,the thermogravimetric kinetic of CS pyrolysis was studied using combined kinetic analysis.It was found that three-parallel-reaction model allowed better fitting relevance for CS pyrolysis.This information was important for simulating and predicting the pyrolysis behaviors of CS.
基金the Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior-Brasil(CAPES)-Finance Code 001.The authors would like to thank the Fundacao de Amparo a Pesquisa do Estado de Sao Paulo-FAPESP(grant number:2021/00251-0).Finally,the authors are also greatly thankful for FIRE support to carry out this work.
文摘Refractories have unique capabilities such as sustaining their shape and properties at extreme conditions such as the combination of high temperatures and thermal shock,contact with molten metals and slags and in some circumstances resistance to erosion from abrasive particles.Given the large processing output of the heavy industries such as the cement and steel ones which both require high temperature processes,the refractories structures span various meters and weight of several tons.As the water removal stage of hydraulic bonded castables in industrial sites takes hours(10-60 h)due to the risk of explosive spalling,efforts to mitigate it are commonly studied.This has provided theoretical understanding of the general aspects of drying and important tools,such as the thermogravimetry analysis(TGA),for the design of refractory compositions with higher explosive spalling resistance.However,the optimization of this process is still far from the industrial reality especially because the actual linings that require the drying are orders of magnitude larger than the samples considered in the laboratory tests.Therefore,this study proposed the analysis of the sample volume effect on the water removal dynamics through TGA of high alumina castables with calcium aluminate cement.Conventionalφ5 cm×5 cm cylindrical samples were assessed in a laboratory scale equipment whereas macro TGA were carried out considering 20 cm×20 cm×20 cm and 30 cm×30 cm×30 cm cubic samples.Additionally,the effect of polymeric fibers was also considered.It was found out that the different thermal gradients within the macro TGA samples resulted in an inflection on the sample’s heating rate and that the mass loss was affected by the volume considered,especially for the composition without additives.These findings highlight the requirement of carefully taking into consideration the different dimensional sizes and thermal gradients in the samples when analyzing and interpreting the laboratory studies,and especially when trying to extrapolate such results to the industrial reality.
文摘Despite the fact that a few countries in the Mediterranean and the Middle East have limited crude oil reserves, they have abundant biomass feedstocks. For instance, Jordan relies heavily on the importation of natural gas and crude oil for its energy needs;but, by applying thermochemical conversion techniques, leftover olive oil can be used to replace these energy sources. Understanding the chemical, physical, and thermal characteristics of raw materials is essential to obtaining the most out of these conversion processes. Thermogravimetric analysis was used in this study to examine the thermal behavior of olive-solid residue (kernel) at three different heating rates (5, 20 and 40 C/min) in nitrogen and oxygen atmospheres. The initial degradation temperature, the residual weight at 500 and 700˚C and the thermal degradation rate during the devolatilization stage (below 400˚C) were all determined. It was found that in N<sub>2</sub> and O<sub>2</sub> atmospheres, both the initial degradation temperature and the degradation rate increase with increasing heating rates. As heating rates increase in the N<sub>2</sub> atmosphere, the residual weight at 500 or 700˚C decreases slightly, but at low heating rates compared to high heating rates in the O<sub>2</sub> atmosphere, it decreases significantly. This suggests that a longer lignin oxidation process is better than a shorter one. Coats and Redfern approach was used to identify the mechanism and activation energy for the devolatilization stage of pyrolysis and oxidation reactions. The process mechanism analysis revealed that the model of first-order and second-order reactions may adequately describe the mechanism of heat degradation of the devolatilization step of olive-solid waste for pyrolysis and oxidation processes, respectively.
基金Project (2006BAK04B03) supported by the National Science and Technology Pillar Program during the 11th Five-Year Plan Period of ChinaProject (kjdb200902-7) supported by Doctoral Candidate Innovation Research Support Program of Science & Technology Review, China+1 种基金Project (1960-71131100023) supported by Postgraduate Dissertation Innovation Foundation of Central South University, ChinaProject (ZKJ2009008) supported by Precious Apparatus Opening Center Foundation of Central South University, China
文摘In order to evaluate the spontaneous combustion hazard of sulfide concentrates in storage, three different kinds of sulfide concentrates （sulfur-rich sulfide concentrate, iron sulfide concentrate and copper sulfide concentrate） were obtained from a storage yard in Dongguashan Copper Mine, China. The reaction processes at different heating rates of 5, 10, 15, 20, and 25 ℃/min in air flow from ambient temperature to 1 000 ℃ were studied by TG-DTG-DSC analysis. By the peak temperatures of DTG curves, the whole reaction process for each sample was divided into different stages, and the corresponding apparent activation energies were calculated by the Ozawa-Flynn-Wall method. It is found that the reaction process of each sample is considerably complex; the apparent activation energy values change from 36 to 160 kJ/mol in different temperature ranges; sulfur-rich sulfide and iron sulfide concentrates have lower apparent activation energy than copper sulfide concentrate below 150 ℃; so they are more inclined to cause spontaneous combustion at ambient temperature.
基金Project (11032010) supported by Key Project of National Natural Science Foundation of ChinaProjects (51072171, 61274107, 61176093, 11275163) supported by the National Natural Science Foundation of China+3 种基金Project (IRT1080) supported by Program for Changjiang Scholars and Innovation Research Team in UniversityProject (2012CB326404) supported by National Basic Research Program of ChinaProject (CX2011B248) supported by Hunan Provincial Innovation Foundation for PostgraduateProject (20104301110001) supported by the Doctoral Program of Higher Education of China
文摘Bi0.9La0.1Fe0.95Mn0.05O3 （BLFMO） ferroelectric thin films were fabricated on Pt/Ti/SiO2/Si/ substrates by the sol-gel process at different pyrolysis temperatures. The mass loss of BLFMO powder was investigated by thermo gravimetry analyser （TGA）, and the polycrystalline structure and smooth surface of BLFMO thin films were characterized by X-ray diffraction （XRD） and atomic force microscopy （AFM）, respectively. The remnant polarization （Pr） of the BLFMO films pyrolyzed at 420 ℃ is 21.2 μC/cm2 at the coercive field （Ec） of 99 kV/cm and the leakage current density is 7.1×10-3 A/cm2, which indicates that the BLFMO thin films display relatively good ferroelectric property at this temperature.
基金Supported by the National Natural Science Foundation of China （No.20376014） and Fujian Science and Technology Council Grant （HG99-01）.
文摘CO2 gasification of Fuijian high-metamorphous anthracite with black liquor （BL） and/or mixture of BL and calcium stuff （BL＋Ca） as catalyst was studied by using a thermogravimetry under 750-950℃ at ambient pressure. When the coal was impregnated with an appropriate quantity of Ca and BL mixture, the catalytic activity of CO2 gasification was enhanced obviously. With a loading of 8%Na-BL＋2%Ca, the carbon conversion of three coal samples tested reaches up to 92.9%-99.3% at 950℃ within 30min. The continuous formation of alkali surface compounds such as （[-COM], [-CO2M]） and the presence of exchanged Ca, such as calcium phenolate and calcium carboxylates （COO）2Ca, contribute to the increase in catalytic efficiency, and using BL＋Ca is more efficient than that adding BL only, The homogeneous model and shrinking-core model were applied to correlate the data of conversion with time and to estimate the reaction rate constants under different temperature. The corresponding reaction activation energy （Ea） and pre-exponential factor of three anthracites were estimated. It is found that Ea is in the range from 73.6 to 121.4kJ·mol^-1 in the case of BL＋Ca, and 74.3 to 104.2kJ·mol^-1 when only BL was used as the catalyst, both of which are much less than that from 143.5 to 181.4kJ·mol^-1 if no catalyst used. It is clearly demonstrated that both of BL＋Ca mixture and BL could be the source of cheap and effective catalyst for coal gasification.
基金Supported by the National Natural Science Foundation of China （20376014） and Fujian Science and Technology Council Grant （HG99-01 ）.
文摘The catalytic effects of single and mixed catalysts, i.e. single 3%Ca and 5%Na-BL（black liquor） catalysts and mixed 3%Ca＋5%Na-BL catalyst, on carbon conversion, gasification reaction rate constant and activation energy, relative amount of harmful pollutant like sulphur containing gases have been investigated by thermogravimetry in steam gasification under temperature 750℃ to 950℃ at ambient pressure for three high-metarnorphous anthracites （Longyan, Fenghai and Youxia coals in Fujian Province）. The mixed catalyst of 3%Ca＋5%Na-BL increases greatly the carbon conversion and gasification rate constant by accelerating the gasification reaction C＋H2O→CO＋H2 due to presence of alkali surfacecompounds [COM], [CO2M] and exchanged calcium phenolate and calcium carboxylate （-COO）2. By adding CaCO3 into BL catalyst in gasification, in addition to improving the catalyst function and enhancing the carbon conversion, the effective desulphurization is also achieved, but the better operating temperature should be below 900℃. The homogenous and shrinking core models can be successfully employed to correlate the relations between the conversion and the gasification .time .and to estimate the reaction rate constant, The reaction acUvaUon energy and pre-exponential factor are estimated and the activation energy for mixed catalyst is in a range of 98.72-166.92 kJ·mol^-1, much less than 177.50-196.46 kJ·mol^-1 for non-catalytic steam gasification for three experimental coals.
基金Sponsored by National Key Technology Research and Development Program of China(2008BAB32B05)Postdoctoral Science Foundation of China(2012m510320)
文摘The kinetics of isothermal reduction of the carbon bearing pellets, which were mainly composed of Bayanobo complex iron ore and pulverized coal, was investigated by thermogravimetry at the temperature of 1 273-1 673 K. The effects of xC/xO and the atmospheres on the extent of reduction also were investigated. The results indicate that the fractional reaction increased proportionally with temperature increasing and heating temperature is the significant influence factor to the reaction of carbon bearing pellets. The optimum xC/xO is 1.2 and the effect of atmosphere on the reduction of iron oxides is almost negligible. The results can be interpreted that the reaction was initially controlled by a mixed controlled mechanism of carbon gasification and interface chemical reaction, and in the later stage, interface chemical reaction became the rate-controlling step. Apparent activation energy values of reduction at different levels of fractional reaction were calculated. Before F （fraction of reaction）=0.5, the apparent activation energy ranges from 66.39 to 75.64 kJ/mol, while after F=0.5, the apparent activation energy is 80.98 to 85.37 kJ/mol.
文摘A novel potential tridentate Schiff base was prepared by condensing equimolar quantities of 2-hydroxyacetophenone and 2-aminopyrimidine in methanol. This ligand was versatile in forming a series of complexes with lanthanide ions such as La（III）, Pr（III）, Nd（III）, Sm（III）, Gd（III）, Dy（III） and Yb（III）. The ligand and the metal complexes were characterized through elemental analysis, molar conductance, UV-Visible, IR, 1H NMR, and mass spectral studies. The spectral studies indicated that the ligand was coordinated to the metal ion in neutral tridentate fashion through the azomethine nitrogen, one of the nitrogen atoms in the pyrimidine ring and the phenolic oxygen without deprotonation. Thermal decomposition and luminescence property of lanthanum（III） complex were also examined. The X-ray diffraction patterns showed the crystalline nature of the ligand and its lanthanum（III） complex. The DNA cleavage studies of the ligand and the metal complexes were carried out and it was observed that the lanthanum（III） and neo-dymium（III） complexes cleaved the pUC19 DNA effectively. The ligand and the metal complexes were screened for their antibacte-rial activities. The metal complexes were found to be more potent bactericides than the ligand.
基金financially supported by the National Natu ral Science Foundation of China (No. U1960205)。
文摘High-phosphorus iron ore resource is considered a refractory iron ore because of its high-phosphorus content and complex ore phase structure. Therefore, the development of innovative technology to realize the efficient utilization of high-phosphorus iron ore resources is of theoretical and practical significance. Thus, a method for phosphorus removal by gasification in the hydrogen-rich sintering process was proposed. In this study, the reduction mechanism of phosphorus in hydrogen-rich sintering, as well as the reduction kinetics of apatite based on the non-isothermal kinetic method, was investigated. Results showed that, by increasing the reduction time from 20 to 60 min, the dephosphorization rate increased from 10.93%to 29.51%. With apatite reduction, the metal iron accumulates, and part of the reduced phosphorus gas is absorbed by the metal iron to form stable iron-phosphorus compounds, resulting in a significant reduction of the dephosphorization rate. Apatite reduction is mainly concentrated in the sintering and burning zones, and the reduced phosphorus gas moves downward along with flue gas under suction pressure and is condensed and adsorbed partly by the sintering bed when passing through the drying zone and over the wet zone. As a result, the dephosphorization rate is considerably reduced. Based on the Ozawa formula of the iso-conversion rate, the activation energy of apatite reduction is 80.42 kJ/mol. The mechanism function of apatite reduction is determined by a differential method (i.e., the Freeman-Carroll method) and an integral method (i.e., the Coats-Redfern method). The differential form of the equation is f(α)=2(1-α)^(1/2), and the integral form of the equation is G(α)=1-(1-α)^(1/2).
基金Project(20574020) supported by the National Natural Science Foundation of China
文摘The flammability characterization and thermal composition of polymers flame retarded by decabromodiphenylethane (DBDPE) and antimony trioxide (Sb2O3) were studied by cone calorimeter and thermogravimetry (TG). The results show that ABS/DBDPE/Sb2O3 has the similar flammability parameters and thermal composition curves to ABS/DBDPO/Sb2O3. It suggests that DBDPE/Sb2O3 has the similar flame retardant behavior to DBDPO/Sb2O3. The heat release rate (HRR) and the effect heat combustion (EHC) curves of polymers flame retarded by DBDPE/Sb2O3 all decrease, but the mass loss rate (MLR) curve slightly increase. It shows that the decrease of HRR is not due to the increase of char formation ratio but the generation of incombustible gases. The major flame retardant mechanism of DBDPE/Sb2O3 is gas phase flame retardant mechanism. Increasing content of Sb2O3 in DBDPE/Sb2O3 can improve the flame retardant property and thermal stability of acrylonitrile butadiene styrene. Sb2O3 has a good synergistic effect with DBDPE.
基金Project supported by the Natural Science Foundation of Henan Province(0511053400)
文摘The oxygen adsorption/desorption properties of double perovskite structure oxides PrBaCo2O5＋δ,GdBaCo2O5＋δ,and YBaCo2O5＋δ were investigated by the thermogravimetry（TG）method in the temperature range of 400~900 ℃.The calculated oxygen adsorption/desorption surface reaction rate constants ka and kd of these double perovskite structure oxides were larger than the commonly used cubic perovskite oxides,such as Ba0.95Ca0.05Co0.8Fe0.2O3-δ and Ba0.5Sr0.5Co0.8Fe0.2O3-δ,whereas,the oxygen permeation flux was comparable to that of the latter,which was attributed to the smaller difference of oxygen vacancy in oxygen and nitrogen atmosphere（Δδ/Vmol）in these double perovskite structure oxides.The large oxygen adsorption/desorption rate constants of GdBaCo2O5＋δ and PrBaCo2O5＋δ made them nice catalyst coating materials,on other membrane surfaces,to improve the oxygen permeability.
基金supported by the Beijing Jiaotong University (Grant C15JB00080)
文摘Phase-field modeling approach has been used to study the oxidation behavior of pure Ni when considering heat conduction. In this calculation, the dependence of the coefficient of the Cahn–Hilliard equation Lc on the temperature T was considered. To this end, high-temperature oxidation experiments and phase-field modeling for pure Ni were performed in air under atmospheric pressure at 600,700, and 800？C. The oxidation rate was measured by thermogravimetry and Lc at these temperatures was determined via interactive algorithm. With the Lc-T relationship constructed, oxidation behavior of Ni when considering heat conduction was investigated. The influence of temperature boundaries on the oxidation degree, oxide film thickness, and specific weight gain were discussed. The phase-field modeling approach proposed in this study will give some highlights of the oxidation resistance analysis and cooling measures design of thermal protection materials.
基金Support of this work by Shahid Chamran University,Ahvaz,Iran and Science&Research Branch,Islamic Azad University,Ahvaz,Iran is gratefully acknowledged
文摘Three new transition metal complexes have been synthesized with a Schiff base, 3-（2-hydroxy-5-chlorophenylimino）-1,3- diphenylpropen-l-one. In all complexes Schiff base is completely deprotonated and coordinated to metal as tridentate ligand via phenolic and enolic oxygens and imine nitrogen. Thermal decomposition of the complexes has been studied by thermogravimetry. The in vitro antibacterial activity of Schiff bases and their complexes has been evaluated and compared with the standard drugs.
基金Projects 2004CB217704 supported by the Special Fund for Major State Basic Research Project, 104031 by the Key Project of Chinese Ministry of Education JHB05-33 by the Program of the Universities in Jiangsu Province for Development of High-Tech Industries
文摘Five Shenfu char samples were prepared from Shenfu raw coal at different temperatures （950, 1100, 1200, 1300 and 1400℃） using a muffle furnace. Demineralization of the char samples was performed by treating them with 10% nitric acid for 10 min in a CEM Discover microwave reactor. The gasification of the chars, and corresponding demineralized chars, in a carbon dioxide （CO2） atmosphere was conducted in a Netzsch STA 409Cl31F tempera- ture-programmed thermogravimetry apparatus. The effects of charring temperature and demineralization on the gasification reactivity of chars were systematically investigated. The results show that a char formed at a lower temperature is more reactive except for demineralized char formed at 1100℃, which is less reactive than char formed at 1200℃. Demineralization decreases the char reactivities toward gasification with CO2 to a small extent.
