In view of the unclear cause of perfluorocarbons(PFCs)emission in the anode effect stage of aluminum electrolysis,the microscopic formation mechanism of PFCs was studied by density functional theory calculation and X-...In view of the unclear cause of perfluorocarbons(PFCs)emission in the anode effect stage of aluminum electrolysis,the microscopic formation mechanism of PFCs was studied by density functional theory calculation and X-ray photoelectron spectroscopy(XPS).It is found that the discharge of fluorine containing anions([F]−)on carbon anode first causes the substitution of C—H by C—F and further results in the saturation of aromatic C—C bonds,leading to the appearance of—CF_(3)or—C_(2)F_(5)group through six-carbon-ring opening.Elimination of—CF_(3)and—C_(2)F_(5) with F atom could be a likely mechanism of CF_(4) and C_(2)F_(6) formation.XPS results confirm that different types of—CF_(x) group can be formed on anode surface during electrolysis,and the possibility that[F]−discharges continuously at the C edge and finally forms different C—F bonds in quantum mechanical calculation was verified.展开更多
Rain-wind-induced vibration of cable was studied based on previous research achievements. According to the quasi-steady assumption, the governing equation of vertical motion of the cable was derived and the criterion ...Rain-wind-induced vibration of cable was studied based on previous research achievements. According to the quasi-steady assumption, the governing equation of vertical motion of the cable was derived and the criterion for unstable motion and occurrence mechanism was studied. A comparison was performed between the oscillation responses of the stay cable obtained from calculated model and previous results. The results indicate that the analysis model can reflect the main characteristics of wind-rain-induced vibrationt of the cable which is amplitude- and velocity-restricted, and it is probably related with the periodic vortex shedding of wake flow. It is essential for the occurrence of rain-wind-induced or wind-induced vibration of cable that the derivative of lift coefficient with respect to transient angle of attack is less than zero. When rain-wind-induced vibration occurs, the aerodynamic force has a dual function for the vibration, and the maximum amplitude of stayed-cable is determined by the relative value of aerodynamic exciting force and aerodynamic damping force.展开更多
Methylphenyldichlorosilane(MPDS, CH3C6H5 SiC l2) is an important silicone monomer for the synthesis of highperformance polymethylphenylsiloxane polymers. In this work, the mechanism of the synthesis of MPDS from methy...Methylphenyldichlorosilane(MPDS, CH3C6H5 SiC l2) is an important silicone monomer for the synthesis of highperformance polymethylphenylsiloxane polymers. In this work, the mechanism of the synthesis of MPDS from methyldichlorosilane and chlorobenzene by gas phase condensation was studied, and a kinetic model with 35 species and 58 elementary reactions was established. Experiments were carried out in a tubular reactor under a wide range of reaction conditions. The calculated mole fractions of the reactants and products were in a good agreement with the experimental results. A mechanism of the insertion of chloromethylsilylene into the C\Cl bond of chlorobenzene was proposed, which was proved to be the main pathway of MPDS production. The established kinetic model can be used in design and optimization of the industrial reactor for MPDS synthesis.展开更多
Phosphorus (P) and metal (M) components were incorporated into promoters for enhancing FCC propylene yield, and the reactive behavior of promoters, before and after modification, were investigated. The results sho...Phosphorus (P) and metal (M) components were incorporated into promoters for enhancing FCC propylene yield, and the reactive behavior of promoters, before and after modification, were investigated. The results showed that both LPG and propylene yields were increased, and propylene selectivity was improved after the incorporation of P or M into the matrix, resulting in an increased C3 to C4 ratio in LPG during FCC process. But the sole incorporation of M into the matrix also led to an increase in coke and H2 yields on the other hand. Simultaneous modification of the matrix by P and M components resulted in more enhancement in propylene yield and selectivity along with little influence on FCC product distribution. Physico-chemical characterizations and model compound reactions were used to assist in analyzing the mechanism for improving propylene selectivity. Two types of active centers could strengthen the oligomerization of C4 olefins in LPG and these oligomers could be further cracked into C3 olefins on ZSM-5 zeolite, therefore maximizing the ratio of C3 to C4 in liquefied petroleum gas obtained during FCC process.展开更多
The physical characteristics of coal reservoirs are important for evaluating the potential for gas desorption, diffusion, and seepage during coalbed methane (CBM) production, and influence the performance of CBM wel...The physical characteristics of coal reservoirs are important for evaluating the potential for gas desorption, diffusion, and seepage during coalbed methane (CBM) production, and influence the performance of CBM wells. Based on data from mercury injection experiments, low-temperature liquid nitrogen adsorption, isothermal adsorption, initial velocity tests of methane diffusion, and gas natural desorption data from a CBM field, herein the physical characteristics of reservoirs of high-rank coals with different coal-body structures are described, including porosity, adsorption/desorption, diffusion, and seepage. Geometric models are constructed for these reservoirs. The modes of diffusion are discussed and a comprehensive diffusion-seepage model is constructed. The following conclusions were obtained. First, the pore distribution of tectonically deformed coal is different from that of normal coal. Compared to normal coal, all types of pore, including micropores (〈10 nm), transitional pores (10-100 nm), mesopores (100-1000 nm), and macropores (〉1000 nm), are more abundant in tectonically deformed coal, especially mesopores and macropores. The increase in pore abundance is greater with increasing tectonic deformation of coal; in addition, the pore connectivity is altered. These are the key factors causing differences in other reservoir physical characteristics, such as adsorption/desorption and diffusion in coals with different coal-body structures. Second, normal and cataclastic coals mainly contain micropores. The lack of macropores and its bad connectivity limit gas desorption and diffusion during the early stage of CBM production. However, the good connectivity of micropores is favorable for gas desorption and diffusion in later gas production stage. Thus, because of the slow decline in the rate of gas desorption, long-term gas production can easily be obtained from these reservoirs. Third, under natural conditions the adsorption/desorption properties of granulated and mylonitized coal are good, and the diffusion ability is also enhanced. However, for in situ reservoir conditions, the high dependence of reservoir permeability on stress results in a weak seepage of gas; thus, desorption and diffusion is limited. Fourth, during gas production, the pore range in which transitional diffusion takes place always increases, but that for Fick diffusion decreases. This is a reason for the reduction in diffusion capacity, in which micropores and transitional pores are the primary factors limiting gas diffusion. Finally, the proposed comprehensive model of CBM production under in situ reservoir conditions elucidates the key factors limiting gas production, which is helpful for selection of reservoir stimulation methods.展开更多
CO2 is a major greenhouse gas,and it can also be used as a chemical feedstock for synthesis of chemicals and fuels by passing the petrochemical source.Herein,we present the recent progress of our research work in the ...CO2 is a major greenhouse gas,and it can also be used as a chemical feedstock for synthesis of chemicals and fuels by passing the petrochemical source.Herein,we present the recent progress of our research work in the catalytic conversion of CO2 to chemicals,with particular attention paid to catalytic reactivity and reaction mechanism.We also give the recommendations regarding the challenges and potential directions of the future research in this field.展开更多
基金the financial supports from the National Natural Science Foundation of China(Nos.51974373,51874365,62133016)the Major Scientific and Technological Innovation Projects of Shandong Province,China(No.2019JZZY020123)the Fundamental Research Funds for the Central Universities of Central South University,China(No.2019zzts242)。
文摘In view of the unclear cause of perfluorocarbons(PFCs)emission in the anode effect stage of aluminum electrolysis,the microscopic formation mechanism of PFCs was studied by density functional theory calculation and X-ray photoelectron spectroscopy(XPS).It is found that the discharge of fluorine containing anions([F]−)on carbon anode first causes the substitution of C—H by C—F and further results in the saturation of aromatic C—C bonds,leading to the appearance of—CF_(3)or—C_(2)F_(5)group through six-carbon-ring opening.Elimination of—CF_(3)and—C_(2)F_(5) with F atom could be a likely mechanism of CF_(4) and C_(2)F_(6) formation.XPS results confirm that different types of—CF_(x) group can be formed on anode surface during electrolysis,and the possibility that[F]−discharges continuously at the C edge and finally forms different C—F bonds in quantum mechanical calculation was verified.
基金Project(51078170) supported by the National Natural Science Foundation of ChinaProject(10JDG097) supported by Jiangsu University Talents Funds,China
文摘Rain-wind-induced vibration of cable was studied based on previous research achievements. According to the quasi-steady assumption, the governing equation of vertical motion of the cable was derived and the criterion for unstable motion and occurrence mechanism was studied. A comparison was performed between the oscillation responses of the stay cable obtained from calculated model and previous results. The results indicate that the analysis model can reflect the main characteristics of wind-rain-induced vibrationt of the cable which is amplitude- and velocity-restricted, and it is probably related with the periodic vortex shedding of wake flow. It is essential for the occurrence of rain-wind-induced or wind-induced vibration of cable that the derivative of lift coefficient with respect to transient angle of attack is less than zero. When rain-wind-induced vibration occurs, the aerodynamic force has a dual function for the vibration, and the maximum amplitude of stayed-cable is determined by the relative value of aerodynamic exciting force and aerodynamic damping force.
文摘Methylphenyldichlorosilane(MPDS, CH3C6H5 SiC l2) is an important silicone monomer for the synthesis of highperformance polymethylphenylsiloxane polymers. In this work, the mechanism of the synthesis of MPDS from methyldichlorosilane and chlorobenzene by gas phase condensation was studied, and a kinetic model with 35 species and 58 elementary reactions was established. Experiments were carried out in a tubular reactor under a wide range of reaction conditions. The calculated mole fractions of the reactants and products were in a good agreement with the experimental results. A mechanism of the insertion of chloromethylsilylene into the C\Cl bond of chlorobenzene was proposed, which was proved to be the main pathway of MPDS production. The established kinetic model can be used in design and optimization of the industrial reactor for MPDS synthesis.
文摘Phosphorus (P) and metal (M) components were incorporated into promoters for enhancing FCC propylene yield, and the reactive behavior of promoters, before and after modification, were investigated. The results showed that both LPG and propylene yields were increased, and propylene selectivity was improved after the incorporation of P or M into the matrix, resulting in an increased C3 to C4 ratio in LPG during FCC process. But the sole incorporation of M into the matrix also led to an increase in coke and H2 yields on the other hand. Simultaneous modification of the matrix by P and M components resulted in more enhancement in propylene yield and selectivity along with little influence on FCC product distribution. Physico-chemical characterizations and model compound reactions were used to assist in analyzing the mechanism for improving propylene selectivity. Two types of active centers could strengthen the oligomerization of C4 olefins in LPG and these oligomers could be further cracked into C3 olefins on ZSM-5 zeolite, therefore maximizing the ratio of C3 to C4 in liquefied petroleum gas obtained during FCC process.
基金supported by the National Natural Science Foundation of China(Grant No.41372162)the Science and Technology Innovation Team Support Plan of Henan Province(Grant No.14IRTSTHN002)
文摘The physical characteristics of coal reservoirs are important for evaluating the potential for gas desorption, diffusion, and seepage during coalbed methane (CBM) production, and influence the performance of CBM wells. Based on data from mercury injection experiments, low-temperature liquid nitrogen adsorption, isothermal adsorption, initial velocity tests of methane diffusion, and gas natural desorption data from a CBM field, herein the physical characteristics of reservoirs of high-rank coals with different coal-body structures are described, including porosity, adsorption/desorption, diffusion, and seepage. Geometric models are constructed for these reservoirs. The modes of diffusion are discussed and a comprehensive diffusion-seepage model is constructed. The following conclusions were obtained. First, the pore distribution of tectonically deformed coal is different from that of normal coal. Compared to normal coal, all types of pore, including micropores (〈10 nm), transitional pores (10-100 nm), mesopores (100-1000 nm), and macropores (〉1000 nm), are more abundant in tectonically deformed coal, especially mesopores and macropores. The increase in pore abundance is greater with increasing tectonic deformation of coal; in addition, the pore connectivity is altered. These are the key factors causing differences in other reservoir physical characteristics, such as adsorption/desorption and diffusion in coals with different coal-body structures. Second, normal and cataclastic coals mainly contain micropores. The lack of macropores and its bad connectivity limit gas desorption and diffusion during the early stage of CBM production. However, the good connectivity of micropores is favorable for gas desorption and diffusion in later gas production stage. Thus, because of the slow decline in the rate of gas desorption, long-term gas production can easily be obtained from these reservoirs. Third, under natural conditions the adsorption/desorption properties of granulated and mylonitized coal are good, and the diffusion ability is also enhanced. However, for in situ reservoir conditions, the high dependence of reservoir permeability on stress results in a weak seepage of gas; thus, desorption and diffusion is limited. Fourth, during gas production, the pore range in which transitional diffusion takes place always increases, but that for Fick diffusion decreases. This is a reason for the reduction in diffusion capacity, in which micropores and transitional pores are the primary factors limiting gas diffusion. Finally, the proposed comprehensive model of CBM production under in situ reservoir conditions elucidates the key factors limiting gas production, which is helpful for selection of reservoir stimulation methods.
基金the financial support from the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA02040602)the National Science&Technology Pillar Program(2013BAC11B02)
文摘CO2 is a major greenhouse gas,and it can also be used as a chemical feedstock for synthesis of chemicals and fuels by passing the petrochemical source.Herein,we present the recent progress of our research work in the catalytic conversion of CO2 to chemicals,with particular attention paid to catalytic reactivity and reaction mechanism.We also give the recommendations regarding the challenges and potential directions of the future research in this field.