A systematic and green low-temperature sulfation roasting−water leaching strategy was put forward to achieve a very high fluorine removal rate of 97.82%for spent carbon cathode(SCC),which was believed as a hazardous s...A systematic and green low-temperature sulfation roasting−water leaching strategy was put forward to achieve a very high fluorine removal rate of 97.82%for spent carbon cathode(SCC),which was believed as a hazardous solid waste.And the carbon could be recycled with a purity of 90.29 wt.%in the flaky microstructure.Thermodynamic analysis and the results of SEM,XRD and EDS indicate that most of the fluoride could convert into water-soluble sulfate at low temperature.And the highest fluorine removal rate could be obtained when<0.15 mm SCC particles were mixed with sulfuric acid at a liquid-to-solid ratio of 1:1,and then roasted at 300℃ for 0.5 h.The sulfate was removed to purify the carbon via water-leaching process.Avrami exponents and corresponding activation energy for the roasting and leaching process demonstrated that both processes are controlled by diffusion.展开更多
To understand the mechanism of fluoride removal from the simulated zinc sulfate solution by the La(III)-modified zeolite,the adsorbent was characterized by XRD,SEM and EDS.The effects of absorbent dose and contact tim...To understand the mechanism of fluoride removal from the simulated zinc sulfate solution by the La(III)-modified zeolite,the adsorbent was characterized by XRD,SEM and EDS.The effects of absorbent dose and contact time,the adsorption isotherms and the sorption kinetics were investigated.The experimental results were compatible with the Langmuir isotherm model.The theoretical maximum adsorption capacities are 20.83 and 23.04 mg/g at 303 and 313 K,respectively.And the physisorption is revealed using the Temkin isotherm model and the D-R isotherm model.The sorption process is more suitable by the pseudo-second-order kinetic models.Thermodynamic parameters such as standard free energy change(ΔGΘ<0 kJ/mol),standard enthalpy change(ΔHΘ=8.28 kJ/mol)and standard entropy change(ΔSΘ=0.030 kJ/(mol?K))indicate the spontaneity of adsorption and endothermic physical sorption.Furthermore,the fluoride concentration in the industrial zinc sulfate solution decreases from 98.05 to 44.09 mg/L with the adsorbent dosage of 15 g/L.展开更多
Deep hydrodesulfurization （HDS） is an important process to produce high quality liquid fuels with ultra-low sul- fur. Process intensification for deep HDS could be implemented by developing new active catalysts and/...Deep hydrodesulfurization （HDS） is an important process to produce high quality liquid fuels with ultra-low sul- fur. Process intensification for deep HDS could be implemented by developing new active catalysts and/or new types of reactors. In this work, the kinetics of dibenzothiophene （DBT） hydrodesulfurization over Ni-P/SBA-15/ cordierite catalyst was investigated at 340-380 ℃ and 3.0-5.0 MPa. The first-order reaction model with respect to both DBT and H2 was used to fit the kinetics data in a batch recycle operation system. It is found that both the activation energy and rate constant over the Ni-P monolithic catalyst under our operating conditions are close to those over conventionally used HDS catalysts. Comparative performance studies of two types of reactors, i.e., trickle bed reactor and monolithic reactor, were performed based on reactor modeling and simulation. The results indicate that the productivity of the monolithic reactor is 3 times higher than that of the trickle bed reactor on a catalyst weight basis since effective utilization of the catalyst is higher in the monolithic reactor, but the volumetric productivity of the monolithic reactor is lower for HDS of DBT. Based on simulation results, a two- reactor-in-series configuration for hydrodesulfurization is proposed, in which a monolithic reactor is followed by a tickled bed reactor so as to attain intensified performance of the system converting fuel oil of different sulfur-containing compounds. It is illustrated that the two reactor scheme outperforms the trickle bed reactor both on reactor volume and catalyst mass bases while the content of sulfur is reduced from 200 μg·g-1 to about 10 μ·g-1.展开更多
The pore structure characteristics of high-sulfur coal from Wansheng in Chongqing have been studied by a nitrogen adsorption method （BET）. The effects of grinding and pre-treating with nitric acid on the inorganic s...The pore structure characteristics of high-sulfur coal from Wansheng in Chongqing have been studied by a nitrogen adsorption method （BET）. The effects of grinding and pre-treating with nitric acid on the inorganic sulfur content of coal have been investigated. Organic sulfur in coal pretreated with nitric acid was desulfurized by using propylene-glycol-KOH （PG-KOH）. Fractal kinetic properties of these two desulfurization procedures were investigated by using fractal geometric theory. The results show that both the specific surface area and pore volume increased with the decrease in particle diameter. The microspore surface of coal had fractal characteristics; the fractal dimension was 2.48. The sulfur content decreased with the decrease in particle diameter by grinding. After pretreatment with nitric acid, the desulfurization ratio （DFR） of inorganic sulfur increased to over 99% and the DFR of total sulfur to over 70%. The desulfurization procedure of inorganic sulfur had fractal kinetic characteristics; its reactive frac- tal dimension was 2.94. The organic sulfur desulfurization procedure by PG-KOH was also tallied with fractal kinetic properties; the reactive fracta! dimension was 2.57. The effect of temperature on the desul- furization ratio of organic sulfur can be described with an Arrhenius empirical equation. The rate constant, pre-exponential factor and the activation energy of the reaction increased with the decrease in particle diameter.展开更多
Desulfurization experiments of CuO, γ-Al2O3 and CuO/γ-Al2O3 were made in simulated flue gas by means of thermogravimetric analysis. It is found that reaction activities of CuO supported on γ-Al2O3 could be highly i...Desulfurization experiments of CuO, γ-Al2O3 and CuO/γ-Al2O3 were made in simulated flue gas by means of thermogravimetric analysis. It is found that reaction activities of CuO supported on γ-Al2O3 could be highly improved. Desulfurization kinetics of CuO/γ-Al2O3 was studied in the temperature range of 250 °C-400 °C and SO2 concentration of 0.1%-0.9%. The experimental data were tested and compared with kinetics models of volume reaction model(VRM), grain size model(GSM), random pore model(RPM) and pore-blocking model(PBM). Correlation analysis shows that VRM and RPM models do not fit experimental data well. GSM contradicts with the changes in the physical and chemical properties of Cu O/γ-Al2O3 as the desulfurization proceeds. It is found that PBM is consistent with the change of pore structure of CuO/γ-Al2O3 sorbent during desulfurization process and predicts the conversion-time curves of the sorbent well. Meanwhile, kinetics parameters are obtained and discussed.展开更多
In this study,by means of the experiments for desulfurization of model diesel through oxidative extraction,the changes associated with the rate of desulfurization of diesel and the mechanism for oxidation of sulfides ...In this study,by means of the experiments for desulfurization of model diesel through oxidative extraction,the changes associated with the rate of desulfurization of diesel and the mechanism for oxidation of sulfides in diesel were explored. Through studying the mechanism for oxidation of sulfides and the principle of solvent extraction,the kinetic equation of desulfurization via oxidative extraction were determined. By means of the evaluation of model parameters and curve fitting,the reaction order between organic sulfide and sulfone,the intrinsic oxidation rate constant of organic sulfide and sulfone,and the equilibrium constant between sulfone in model diesel and extractive solvent were determined. The experimental values of the desulfurization rate and the theoretical values of the corresponding model equation had closely demonstrated that the desulfurization reaction rate had high accuracy. And the reaction kinetics could provide an important basis for diesel desulfurization process in the future.展开更多
基金the Natural Science Foundation of Hunan Province,China(No.2020JJ1007).
文摘A systematic and green low-temperature sulfation roasting−water leaching strategy was put forward to achieve a very high fluorine removal rate of 97.82%for spent carbon cathode(SCC),which was believed as a hazardous solid waste.And the carbon could be recycled with a purity of 90.29 wt.%in the flaky microstructure.Thermodynamic analysis and the results of SEM,XRD and EDS indicate that most of the fluoride could convert into water-soluble sulfate at low temperature.And the highest fluorine removal rate could be obtained when<0.15 mm SCC particles were mixed with sulfuric acid at a liquid-to-solid ratio of 1:1,and then roasted at 300℃ for 0.5 h.The sulfate was removed to purify the carbon via water-leaching process.Avrami exponents and corresponding activation energy for the roasting and leaching process demonstrated that both processes are controlled by diffusion.
基金Projects(51474238,51674301)supported by the National Natural Science Foundation of China
文摘To understand the mechanism of fluoride removal from the simulated zinc sulfate solution by the La(III)-modified zeolite,the adsorbent was characterized by XRD,SEM and EDS.The effects of absorbent dose and contact time,the adsorption isotherms and the sorption kinetics were investigated.The experimental results were compatible with the Langmuir isotherm model.The theoretical maximum adsorption capacities are 20.83 and 23.04 mg/g at 303 and 313 K,respectively.And the physisorption is revealed using the Temkin isotherm model and the D-R isotherm model.The sorption process is more suitable by the pseudo-second-order kinetic models.Thermodynamic parameters such as standard free energy change(ΔGΘ<0 kJ/mol),standard enthalpy change(ΔHΘ=8.28 kJ/mol)and standard entropy change(ΔSΘ=0.030 kJ/(mol?K))indicate the spontaneity of adsorption and endothermic physical sorption.Furthermore,the fluoride concentration in the industrial zinc sulfate solution decreases from 98.05 to 44.09 mg/L with the adsorbent dosage of 15 g/L.
基金Supported by the State Key Development Program for Basic Research of China(2006CB202503)
文摘Deep hydrodesulfurization （HDS） is an important process to produce high quality liquid fuels with ultra-low sul- fur. Process intensification for deep HDS could be implemented by developing new active catalysts and/or new types of reactors. In this work, the kinetics of dibenzothiophene （DBT） hydrodesulfurization over Ni-P/SBA-15/ cordierite catalyst was investigated at 340-380 ℃ and 3.0-5.0 MPa. The first-order reaction model with respect to both DBT and H2 was used to fit the kinetics data in a batch recycle operation system. It is found that both the activation energy and rate constant over the Ni-P monolithic catalyst under our operating conditions are close to those over conventionally used HDS catalysts. Comparative performance studies of two types of reactors, i.e., trickle bed reactor and monolithic reactor, were performed based on reactor modeling and simulation. The results indicate that the productivity of the monolithic reactor is 3 times higher than that of the trickle bed reactor on a catalyst weight basis since effective utilization of the catalyst is higher in the monolithic reactor, but the volumetric productivity of the monolithic reactor is lower for HDS of DBT. Based on simulation results, a two- reactor-in-series configuration for hydrodesulfurization is proposed, in which a monolithic reactor is followed by a tickled bed reactor so as to attain intensified performance of the system converting fuel oil of different sulfur-containing compounds. It is illustrated that the two reactor scheme outperforms the trickle bed reactor both on reactor volume and catalyst mass bases while the content of sulfur is reduced from 200 μg·g-1 to about 10 μ·g-1.
文摘The pore structure characteristics of high-sulfur coal from Wansheng in Chongqing have been studied by a nitrogen adsorption method （BET）. The effects of grinding and pre-treating with nitric acid on the inorganic sulfur content of coal have been investigated. Organic sulfur in coal pretreated with nitric acid was desulfurized by using propylene-glycol-KOH （PG-KOH）. Fractal kinetic properties of these two desulfurization procedures were investigated by using fractal geometric theory. The results show that both the specific surface area and pore volume increased with the decrease in particle diameter. The microspore surface of coal had fractal characteristics; the fractal dimension was 2.48. The sulfur content decreased with the decrease in particle diameter by grinding. After pretreatment with nitric acid, the desulfurization ratio （DFR） of inorganic sulfur increased to over 99% and the DFR of total sulfur to over 70%. The desulfurization procedure of inorganic sulfur had fractal kinetic characteristics; its reactive frac- tal dimension was 2.94. The organic sulfur desulfurization procedure by PG-KOH was also tallied with fractal kinetic properties; the reactive fracta! dimension was 2.57. The effect of temperature on the desul- furization ratio of organic sulfur can be described with an Arrhenius empirical equation. The rate constant, pre-exponential factor and the activation energy of the reaction increased with the decrease in particle diameter.
基金Projects(51264023,51364020,U1202271)supported by the National Natural Science Foundation of ChinaProject(IRT1250)supported by the Program for Innovative Research Team in University of Ministry of Education of ChinaProject(2014HA003)supported by the Yunnan Province Science and Technology Talents Program,China
文摘Desulfurization experiments of CuO, γ-Al2O3 and CuO/γ-Al2O3 were made in simulated flue gas by means of thermogravimetric analysis. It is found that reaction activities of CuO supported on γ-Al2O3 could be highly improved. Desulfurization kinetics of CuO/γ-Al2O3 was studied in the temperature range of 250 °C-400 °C and SO2 concentration of 0.1%-0.9%. The experimental data were tested and compared with kinetics models of volume reaction model(VRM), grain size model(GSM), random pore model(RPM) and pore-blocking model(PBM). Correlation analysis shows that VRM and RPM models do not fit experimental data well. GSM contradicts with the changes in the physical and chemical properties of Cu O/γ-Al2O3 as the desulfurization proceeds. It is found that PBM is consistent with the change of pore structure of CuO/γ-Al2O3 sorbent during desulfurization process and predicts the conversion-time curves of the sorbent well. Meanwhile, kinetics parameters are obtained and discussed.
文摘In this study,by means of the experiments for desulfurization of model diesel through oxidative extraction,the changes associated with the rate of desulfurization of diesel and the mechanism for oxidation of sulfides in diesel were explored. Through studying the mechanism for oxidation of sulfides and the principle of solvent extraction,the kinetic equation of desulfurization via oxidative extraction were determined. By means of the evaluation of model parameters and curve fitting,the reaction order between organic sulfide and sulfone,the intrinsic oxidation rate constant of organic sulfide and sulfone,and the equilibrium constant between sulfone in model diesel and extractive solvent were determined. The experimental values of the desulfurization rate and the theoretical values of the corresponding model equation had closely demonstrated that the desulfurization reaction rate had high accuracy. And the reaction kinetics could provide an important basis for diesel desulfurization process in the future.
