This work evaluated the effects of inherent alkali and alkaline earth metals on nitrogen transformation during steam gasification of Shengli lignite at the temperature of 873-1173 K in a fluidized-bed/fixed-bed quartz...This work evaluated the effects of inherent alkali and alkaline earth metals on nitrogen transformation during steam gasification of Shengli lignite at the temperature of 873-1173 K in a fluidized-bed/fixed-bed quartz reactor. The results indicated that the alkali metal Na and alkaline earth metals Ca, Mg in coal have different effects on inherent nitrogen transformation to NH3, HCN and char-N during the lignite steam gasification. Specifically during the steam gasification of Shengli lignite, Na and Ca, Mg not only catalyze the inherent nitrogen conversions to NH3, but also promote the secondary reactions of the nascent char-N as well as the generation of NH3 from the generated HCN, meanwhile they also inhibited the inherent nitrogen conversion to HCN and char-N. The presence of Na, Ca and Mg hindered the formation of oxidized nitrogen (N-X) functional groups, but enhanced pyridinic nitrogen (N-6) and quaternary nitrogen's (N-Q) formation in char.展开更多
The occurrence modes of alkali and alkaline-earth metals（AAEMs） in coal relate to their release behavior and ash formation during combustion. To better understand the transformation of AAEMs,the release behavior of ...The occurrence modes of alkali and alkaline-earth metals（AAEMs） in coal relate to their release behavior and ash formation during combustion. To better understand the transformation of AAEMs,the release behavior of water-soluble,HCl-soluble,HCl-insoluble AAEMs during Shenmu coal（SM coal） oxy-fuel combustion in the presence of SO2 and H2O in a drop-tube reactor was investigated through serial dissolution using H2O and HCl solutions. The results show that the release rates of AAEMs increase with an increase in temperature under the three atmospheres studied. The high release rates of Mg and Ca from SM coal are dependent on the high content of soluble Mg and Ca in SM coal. SO2 inhibits the release rates of AAEMs,while H2O promotes them. The effects of SO2 and H2O on the Na and K species are more evident than those on Mg and Ca species. All three types of AAEMs in coal can volatilize in the gas phase during coal combustion. The W-type AAEMs release excessively,whereas the release rates of I-type AAEMs are relatively lower. Different types of AAEM may interconvert through different pathways under certain conditions. Both SO2 and H2O promote the transformation reactions. The effect of SO2 was related to sulfate formation and the promotion by H2O occurs because of a decrease in the melting point of the solid as well as the reaction of H2O.展开更多
In this paper, the interaction parameters in the subregular solution model, λ1 and λ2, are regarded as a linear function of temperature, T. Therefore, the molar excess Gibbs energy of A-B binary system may be reexpr...In this paper, the interaction parameters in the subregular solution model, λ1 and λ2, are regarded as a linear function of temperature, T. Therefore, the molar excess Gibbs energy of A-B binary system may be reexpressed as follows:Gm^E=xAxB[(λ11+λ12T)+(λ21+λ22T)xB]The calculation of the model parameters, λ11, λ12, λ21and λ22, was carried out numerically from the phase diagrams for 11 alkali metal-alkali halide or alkali earth metal-halide systems. In addition, artificial neural network trained by known data has been used to predict the values of these model parameters. The predicted results are in good agreement with the .calculated ones. The applicability of the subregular solution model to the alkali metal-alkali halide or alkali earth metal-halide systems were tested by comparing the available experimental composition along the boundary of miscibility gap with the calculated ones which were obtained by using genetic algorithm. The good agreement between the calculated and experimental results across the entire liquidus is valid evidence in support of the model.展开更多
The three dimensional EHMO crystal orbital calculations for crystalline Ba6 C60,Ca3 C60 and Ca5 C60 are reported.The ground state of partially doped Ca3 C60 is found to be insulating with an indrect energy gap of 0.5e...The three dimensional EHMO crystal orbital calculations for crystalline Ba6 C60,Ca3 C60 and Ca5 C60 are reported.The ground state of partially doped Ca3 C60 is found to be insulating with an indrect energy gap of 0.5eV.In contrast,the Ca5 C60 forms a metallic conducting phase with a set of three half-filled bands crossing the Fermi level which is Found to locate close to a peak of the density of state. The character of crystal orbitals near the Fermilevel for both Ca3 C60 and Ca5 C60 is completely carbon-like.In both cases the Ca3 atoms are almost fully ionized and C60 molecules form a stable negative charge state with six to ten additional electrons.The conductivity of Ba6 C60 is resuted from the incomplete charge tranfer.The valance charge of every Ba ion is about 0.33.The total charge tranfer of six Ba atoms is almost the same as that of five Ca atoms.展开更多
The quality of stainless steel is closely related to the deformability of inclusions,which is significantly affected by their compositions.The present study first inve stigated the evolution of inclusion compositions ...The quality of stainless steel is closely related to the deformability of inclusions,which is significantly affected by their compositions.The present study first inve stigated the evolution of inclusion compositions in AI-killed steel with rare earth-alkali metals(Ca or Mg)combined treatme nt through four laboratory-scale experiments.The Ce contents in the final steel are 0.0080 wt%,0.015 wt%,0.016 wt%and 0.010 wt%,respectively.The Mg content is 0.0014 wt%in Ce-Mg combined treated steel,and the Ca content is0.0015 wt%in Ce-Ca combined treated steel.The deformability of inclusions in both Ce_(2)O_(3)-Al_(2)O_(3)-CaO and Ce_(2)O_(3)-Al_(2)O_(3)-MgO systems was subsequently evaluated by calculating their Young's modulus at low temperature.The results show that irregular Al_(2)O_(3)and MgAl_(2)O_(4)with poor deformability are modified to CeAlO_(3)and Ce_(2)O_(3)by Ce treatment,resulting in the decrease of Young's modulus of inclusions.The deformability of inclusions is further improved due to the transformation from lumped-like CeAlO_(3)to spherical CaO-Al_(2)O_(3)-Ce_(2)O_(3)caused by Ca treatment,and some of these inclusions are the ones with low liquidus temperature.Thermodynamic analysis was used to discuss the control condition of the formation and evolution of inclusions.Accordingly,the appropriate addition amounts of Al,Mg,Ce,and Ca are expected to control inclusion compositions and properties,including deformability and liquidus temperature,thereby improving the steel performance.展开更多
The recent results on hydrothermal synthesis of mixed rare earth-alkali or ammonium fluorides were presented. The initial ratios of the starting materials, pH value and reaction temperature were the critical factors f...The recent results on hydrothermal synthesis of mixed rare earth-alkali or ammonium fluorides were presented. The initial ratios of the starting materials, pH value and reaction temperature were the critical factors for obtaining the single-phase product. Four main types of complex rare earth fluorides, AREF4, A2REF5, ARE2F7 and ARE3F10 (A=Na+, K+, Rb+, NH4+), appeared in the primary hydrothermal reactions. The correlation between cation sizes and the formation of mixed rare earth fluorides under mild hydro...展开更多
基金The authors gratefully acknowledge the financial support provided by the 12th Five-Year Plan of National Science and Technology Support (Grant 2012BAA04B02)the National Natural Science Foundation of China (No.21406261).
文摘This work evaluated the effects of inherent alkali and alkaline earth metals on nitrogen transformation during steam gasification of Shengli lignite at the temperature of 873-1173 K in a fluidized-bed/fixed-bed quartz reactor. The results indicated that the alkali metal Na and alkaline earth metals Ca, Mg in coal have different effects on inherent nitrogen transformation to NH3, HCN and char-N during the lignite steam gasification. Specifically during the steam gasification of Shengli lignite, Na and Ca, Mg not only catalyze the inherent nitrogen conversions to NH3, but also promote the secondary reactions of the nascent char-N as well as the generation of NH3 from the generated HCN, meanwhile they also inhibited the inherent nitrogen conversion to HCN and char-N. The presence of Na, Ca and Mg hindered the formation of oxidized nitrogen (N-X) functional groups, but enhanced pyridinic nitrogen (N-6) and quaternary nitrogen's (N-Q) formation in char.
基金support for this research from the Natural Science Foundation of China (U1261110)the Natural Science Foundation of Shanxi Province (20130110422)the Foundation of State Key Laboratory of Coal Combustion (FSKLCC-0914)
文摘The occurrence modes of alkali and alkaline-earth metals（AAEMs） in coal relate to their release behavior and ash formation during combustion. To better understand the transformation of AAEMs,the release behavior of water-soluble,HCl-soluble,HCl-insoluble AAEMs during Shenmu coal（SM coal） oxy-fuel combustion in the presence of SO2 and H2O in a drop-tube reactor was investigated through serial dissolution using H2O and HCl solutions. The results show that the release rates of AAEMs increase with an increase in temperature under the three atmospheres studied. The high release rates of Mg and Ca from SM coal are dependent on the high content of soluble Mg and Ca in SM coal. SO2 inhibits the release rates of AAEMs,while H2O promotes them. The effects of SO2 and H2O on the Na and K species are more evident than those on Mg and Ca species. All three types of AAEMs in coal can volatilize in the gas phase during coal combustion. The W-type AAEMs release excessively,whereas the release rates of I-type AAEMs are relatively lower. Different types of AAEM may interconvert through different pathways under certain conditions. Both SO2 and H2O promote the transformation reactions. The effect of SO2 was related to sulfate formation and the promotion by H2O occurs because of a decrease in the melting point of the solid as well as the reaction of H2O.
文摘In this paper, the interaction parameters in the subregular solution model, λ1 and λ2, are regarded as a linear function of temperature, T. Therefore, the molar excess Gibbs energy of A-B binary system may be reexpressed as follows:Gm^E=xAxB[(λ11+λ12T)+(λ21+λ22T)xB]The calculation of the model parameters, λ11, λ12, λ21and λ22, was carried out numerically from the phase diagrams for 11 alkali metal-alkali halide or alkali earth metal-halide systems. In addition, artificial neural network trained by known data has been used to predict the values of these model parameters. The predicted results are in good agreement with the .calculated ones. The applicability of the subregular solution model to the alkali metal-alkali halide or alkali earth metal-halide systems were tested by comparing the available experimental composition along the boundary of miscibility gap with the calculated ones which were obtained by using genetic algorithm. The good agreement between the calculated and experimental results across the entire liquidus is valid evidence in support of the model.
文摘The three dimensional EHMO crystal orbital calculations for crystalline Ba6 C60,Ca3 C60 and Ca5 C60 are reported.The ground state of partially doped Ca3 C60 is found to be insulating with an indrect energy gap of 0.5eV.In contrast,the Ca5 C60 forms a metallic conducting phase with a set of three half-filled bands crossing the Fermi level which is Found to locate close to a peak of the density of state. The character of crystal orbitals near the Fermilevel for both Ca3 C60 and Ca5 C60 is completely carbon-like.In both cases the Ca3 atoms are almost fully ionized and C60 molecules form a stable negative charge state with six to ten additional electrons.The conductivity of Ba6 C60 is resuted from the incomplete charge tranfer.The valance charge of every Ba ion is about 0.33.The total charge tranfer of six Ba atoms is almost the same as that of five Ca atoms.
基金supported by the National Natural Science Foundation of China-Liaoning Joint Fund (U1908224)。
文摘The quality of stainless steel is closely related to the deformability of inclusions,which is significantly affected by their compositions.The present study first inve stigated the evolution of inclusion compositions in AI-killed steel with rare earth-alkali metals(Ca or Mg)combined treatme nt through four laboratory-scale experiments.The Ce contents in the final steel are 0.0080 wt%,0.015 wt%,0.016 wt%and 0.010 wt%,respectively.The Mg content is 0.0014 wt%in Ce-Mg combined treated steel,and the Ca content is0.0015 wt%in Ce-Ca combined treated steel.The deformability of inclusions in both Ce_(2)O_(3)-Al_(2)O_(3)-CaO and Ce_(2)O_(3)-Al_(2)O_(3)-MgO systems was subsequently evaluated by calculating their Young's modulus at low temperature.The results show that irregular Al_(2)O_(3)and MgAl_(2)O_(4)with poor deformability are modified to CeAlO_(3)and Ce_(2)O_(3)by Ce treatment,resulting in the decrease of Young's modulus of inclusions.The deformability of inclusions is further improved due to the transformation from lumped-like CeAlO_(3)to spherical CaO-Al_(2)O_(3)-Ce_(2)O_(3)caused by Ca treatment,and some of these inclusions are the ones with low liquidus temperature.Thermodynamic analysis was used to discuss the control condition of the formation and evolution of inclusions.Accordingly,the appropriate addition amounts of Al,Mg,Ce,and Ca are expected to control inclusion compositions and properties,including deformability and liquidus temperature,thereby improving the steel performance.
基金financially supported by the National Key Basic Research Program of China(No.2014CB643403)the National Science Fund for Distinguished Young Scholars(No.51225401)
基金Project supported by the National Natural Science Foundation of China (10774012, 10874014 and 10979009)
文摘The recent results on hydrothermal synthesis of mixed rare earth-alkali or ammonium fluorides were presented. The initial ratios of the starting materials, pH value and reaction temperature were the critical factors for obtaining the single-phase product. Four main types of complex rare earth fluorides, AREF4, A2REF5, ARE2F7 and ARE3F10 (A=Na+, K+, Rb+, NH4+), appeared in the primary hydrothermal reactions. The correlation between cation sizes and the formation of mixed rare earth fluorides under mild hydro...
