Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic fram...Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.展开更多
A three-dimensional mathematical model was established to predict the multiphase flow,motion and dispersion of desulfurizer particles,and desulfurization of hot metal during the Kanbara reactor(KR)process.The turbulen...A three-dimensional mathematical model was established to predict the multiphase flow,motion and dispersion of desulfurizer particles,and desulfurization of hot metal during the Kanbara reactor(KR)process.The turbulent kinetic energy-turbulent dissipation rate(k-ε)turbulence model,volume-of-fluid multiphase model,discrete-phase model,and unreacted core model for the reaction between the hot metal and particles were coupled.The measured sulfur content of the hot metal with time during the actual KR process was employed to validate the current mathematical model.The distance from the lowest point of the liquid level to the bottom of the ladle decreased from 3170 to2191 mm when the rotation speed increased from 30 to 110 r/min,which had a great effect on the dispersion of desulfurizer particles.The critical rotation speed for the vortex to reach the upper edge of the stirring impeller was 70 r/min when the immersion depth was 1500 mm.The desulfurization rate increased with the increase in the impeller rotation speed,whereas the influence of the immersion depth was relatively small.Formulas for different rotation parameters on the desulfurization rate constant and turbulent energy dissipation rate were proposed to evaluate the variation in sulfur content over time.展开更多
This paper summarizes the results of a study of adsorption of sulfur compounds from a high-sulfur feed on improved spherical-shaped nano-AgX zeolite. For this purpose, the nano-AgX zeolite was initially synthesized an...This paper summarizes the results of a study of adsorption of sulfur compounds from a high-sulfur feed on improved spherical-shaped nano-AgX zeolite. For this purpose, the nano-AgX zeolite was initially synthesized and improved with silver compounds such as silver nitrate, and then it was utilized in the adsorption process. In order to investigate the equilibrium and dynamics of the adsorption process, adsorptive desulfurization of real feed(i.e., sour gas condensate from the South Pars gas field) was carried out in batch and continuous processes under several operating conditions; a temperature-dependent Langmuir isotherm model was used to fit the equilibrium data. The value of monolayer adsorption capacity(q_m) and adsorption enthalpy(ΔH) were calculated to be 1.044 mmol/g and 16.8 kJ/mol, respectively. Furthermore, a detailed theoretical model was employed in order to model the breakthrough experiments. The results revealed that an increase in the feed flow rate and 1/T values will cause linear and exponential increase in the total mass transfer coefficient(ks). Isotherm and dynamic breakthrough models were found to be in agreement with the experimental data.展开更多
Wet Flue Gas Desulfurization(WFGD)unit based upon spray scrubber has beenwidely employed to control SO_(2) emissions from flue gas in coal-fired power plant.To clarify the dependence of desulfurization performance on ...Wet Flue Gas Desulfurization(WFGD)unit based upon spray scrubber has beenwidely employed to control SO_(2) emissions from flue gas in coal-fired power plant.To clarify the dependence of desulfurization performance on inter-phase transfer behaviors with non-ideal contacting patterns of flue gas and slurry droplets,three regions in spray scrubber are distinguished in terms of gas-slurry flow structures using CFD method in the Eulerian-Lagrangian framework.A comprehensive model is established by involving the transfer process between two phases and chemical reactions in aqueous phase,which is validatedwith the measured data froma WFGD scrubber of 330 MW coal-fired power unit.Numerical results show that the overall uniformity degree of flue gas in whole scrubber is largely determined by the force-balanced droplets in the middle part of scrubber,which is dominated by counter-current mode.Both momentum transfer behavior and SO_(2) chemical absorption process present the synchronicity with the evolution of gas-slurry flow pattern,whilst the heat transfer together with H_(2)O evaporation has little effect on overall absorption process.Three regions are firstly defined as Gas Inlet Region(GIR),Dominant Absorption Region(DAR)and Slurry Dispersed Region(SDR)from the bottom to top of scrubber.SO_(2) is mainly scrubbed in DAR,which provides much more intensive interaction between two phases compared to GIR or SDR.A better understanding of the desulfurization process is obtained from the fundamental relationship between transport phenomena and chemical reactions based upon the complicated hydrodynamics of gas-slurry two-phase flow,which should be useful for designing and optimizing the scrubber in coal-fired power unit.展开更多
Selective flocculation is an idea separation method to separate ultrafine pyrite from coal. A number of selective flocculation separation tests under different conditions have been done and the results are very encour...Selective flocculation is an idea separation method to separate ultrafine pyrite from coal. A number of selective flocculation separation tests under different conditions have been done and the results are very encouraging. The results also show that desulfurization and deashing can be finished simultaneously in selective fIocculation process. It is an advanced coal desulfurization process.展开更多
The Beijing Research lnstitute of Coal Chemistry (BRICC) is developing the SMOVEN process for hot gas desulfurization. The SMOVEN process features sulfidation in an entrained bed,regeneration in a low velocity fluid b...The Beijing Research lnstitute of Coal Chemistry (BRICC) is developing the SMOVEN process for hot gas desulfurization. The SMOVEN process features sulfidation in an entrained bed,regeneration in a low velocity fluid bed or a moving bed with oxygen and sorbent circuIation con-trolled by gas stream. A series of tests on the bench scale unit and the continuous process devel-opment unit were carried out. The regenerable metal oxide sorbents were adopted for the sulfur-related components removing from coal gas at the temperature of 550-650℃. A fluidized bed gasifier of 100 mm (id) generated coal gas for tests. The principle of SMOVEN process has been positively verified.展开更多
An anaerobic expanding-bed reactor was adopted to investigate the feasibility of an innovative integrated process of simultaneous desulfurization and denitrification (SDD) for high strength wastewater. In the reactor,...An anaerobic expanding-bed reactor was adopted to investigate the feasibility of an innovative integrated process of simultaneous desulfurization and denitrification (SDD) for high strength wastewater. In the reactor, heterotrophic bacteria (including sulfate reducing bacterium and denitrifying bacteria) and autotrophic bacteria (including Thiobacillus denitrificans) cooperated together by incubating and enriching functional bacteria on different carriers in the anaerobic activated sludge. Synthetic wastewater with high concentrations of sulfate and nitrate was employed. The experimental results showed that the removal efficiency of sulfate and nitrate was above 85%, elemental sulfur was observed while nitrate was absent in effluent. The balance of sulfur, nitrogen and electron was discussed respectively, which indicated that the integrated SDD process could be actualized. These results might provide a guidance to further investigate the key factors affecting the integrated SDD process and to improve the efficiency of desulfurization and denitrification in wastewater treatment.展开更多
Phosphogypsum(PG) desulfurization slag is a calcium-rich residue from reductive decomposition of PG using sulfur as the reductant. We proposed a technology of preparation light calcium carbonate with PG desulfurizatio...Phosphogypsum(PG) desulfurization slag is a calcium-rich residue from reductive decomposition of PG using sulfur as the reductant. We proposed a technology of preparation light calcium carbonate with PG desulfurization slag, which mainly contains two steps: leaching and carbonizing. In this work, we concentrated on the former, in which ammonium chloride aqueous solution was utilized as leaching agent to extract calcium from the slag, and conducted thermodynamics and kinetics study on it. Fact Sage software was employed to do thermodynamic and phase equilibrium diagram calculations. The influence of leaching conditions including agitation speed, initial concentration of leaching solution, reaction temperature, and liquid/solid ratio on the calcium leaching rate was discussed in detail by means of experiment optimal design. A kinetic model developed from the shrinking core model was given to describe the leaching process. The apparent kinetic activation energy(Ea) of the leaching reaction was calculated to be 10.58 kJ·mol^-1.展开更多
The reactive adsorption behavior of thiophene on the reduced Ni/ZnO sample was investigated by a combination of theoretical and experimental study.It is widely accepted that Ni is responsible for the sulfur-removal of...The reactive adsorption behavior of thiophene on the reduced Ni/ZnO sample was investigated by a combination of theoretical and experimental study.It is widely accepted that Ni is responsible for the sulfur-removal of thiophene to release S-free hydrocarbons.Such surface reaction was simulated by DFT method.It is demonstrated that thiophene is mainly adsorbed as p-complexation mode over metallic Ni.During desulfurization,the Se Ni bond is formed and the Ce S bond is thus split without pre-hydrogenation,resulting in the formation of Ni_(3)S_(2)phase and S-free C4 olefin which can be further saturated in the presence of H_(2).The S-transfer between Ni_(3)S_(2)and ZnO was monitored by in-situ XRD and STEM with EDS mapping.Two essential features were identified for efficient S-transfer,namely,1)the H_(2)atmosphere,and 2)the two phases are presented with close contact.Based on the acquired information,a general scenario of sulfur trail has been proposed for the desulfurization of thiophene on Ni/ZnO.展开更多
脱硫过程是具有高度动态非线性和较大延迟时间的复杂工业过程,为了解决烟气脱硫过程的建模问题,设计了注意力机制下的深度长短期记忆(attention mechanism-based long short-term memory,AttLSTM)网络,并基于该网络设计自动编码器,完成...脱硫过程是具有高度动态非线性和较大延迟时间的复杂工业过程,为了解决烟气脱硫过程的建模问题,设计了注意力机制下的深度长短期记忆(attention mechanism-based long short-term memory,AttLSTM)网络,并基于该网络设计自动编码器,完成脱硫过程异常点的检测。该文首次提出使用AttLSTM网络自编码器对脱硫过程进行离群点检测,并且该网络模型同样首次应用于脱硫过程的辨识任务中。从更深的意义上讲,该文尝试使用深度学习模型对复杂系统进行辨识,所建立的AttLSTM网络之前未出现在系统辨识领域,该网络的出现可以丰富辨识模型的选择,同时为人工智能技术在系统辨识领域和控制领域的应用与推广提供参考。实验结果表明,相比于之前文献出现的脱硫过程建模方法,所提方法在不同性能指标上均具有更好的表现,由此可以证明深度AttLSTM网络在脱硫场景下的有效性。展开更多
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21978119,22202088)Key Research and Development Plan of Hainan Province(ZDYF2022SHFZ285)Jiangsu Funding Program for Excellent Postdoctoral Talent(2022ZB636)。
文摘Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.
基金financially supported by the National Science Foundation China(No.52104343)the Natural Science Foundation of Hebei Province,China(No.E2021203222)+1 种基金support from the High Steel Center(HSC)at Yanshan UniversityNorth China University of Technology,China。
文摘A three-dimensional mathematical model was established to predict the multiphase flow,motion and dispersion of desulfurizer particles,and desulfurization of hot metal during the Kanbara reactor(KR)process.The turbulent kinetic energy-turbulent dissipation rate(k-ε)turbulence model,volume-of-fluid multiphase model,discrete-phase model,and unreacted core model for the reaction between the hot metal and particles were coupled.The measured sulfur content of the hot metal with time during the actual KR process was employed to validate the current mathematical model.The distance from the lowest point of the liquid level to the bottom of the ladle decreased from 3170 to2191 mm when the rotation speed increased from 30 to 110 r/min,which had a great effect on the dispersion of desulfurizer particles.The critical rotation speed for the vortex to reach the upper edge of the stirring impeller was 70 r/min when the immersion depth was 1500 mm.The desulfurization rate increased with the increase in the impeller rotation speed,whereas the influence of the immersion depth was relatively small.Formulas for different rotation parameters on the desulfurization rate constant and turbulent energy dissipation rate were proposed to evaluate the variation in sulfur content over time.
文摘This paper summarizes the results of a study of adsorption of sulfur compounds from a high-sulfur feed on improved spherical-shaped nano-AgX zeolite. For this purpose, the nano-AgX zeolite was initially synthesized and improved with silver compounds such as silver nitrate, and then it was utilized in the adsorption process. In order to investigate the equilibrium and dynamics of the adsorption process, adsorptive desulfurization of real feed(i.e., sour gas condensate from the South Pars gas field) was carried out in batch and continuous processes under several operating conditions; a temperature-dependent Langmuir isotherm model was used to fit the equilibrium data. The value of monolayer adsorption capacity(q_m) and adsorption enthalpy(ΔH) were calculated to be 1.044 mmol/g and 16.8 kJ/mol, respectively. Furthermore, a detailed theoretical model was employed in order to model the breakthrough experiments. The results revealed that an increase in the feed flow rate and 1/T values will cause linear and exponential increase in the total mass transfer coefficient(ks). Isotherm and dynamic breakthrough models were found to be in agreement with the experimental data.
基金This work was supported by the National Natural Science Foundation of China(51706070 and U1910215)the Fundamental Research Funds for the Central Universities(2018ZD03,2020MS008 and 2020MS078).
文摘Wet Flue Gas Desulfurization(WFGD)unit based upon spray scrubber has beenwidely employed to control SO_(2) emissions from flue gas in coal-fired power plant.To clarify the dependence of desulfurization performance on inter-phase transfer behaviors with non-ideal contacting patterns of flue gas and slurry droplets,three regions in spray scrubber are distinguished in terms of gas-slurry flow structures using CFD method in the Eulerian-Lagrangian framework.A comprehensive model is established by involving the transfer process between two phases and chemical reactions in aqueous phase,which is validatedwith the measured data froma WFGD scrubber of 330 MW coal-fired power unit.Numerical results show that the overall uniformity degree of flue gas in whole scrubber is largely determined by the force-balanced droplets in the middle part of scrubber,which is dominated by counter-current mode.Both momentum transfer behavior and SO_(2) chemical absorption process present the synchronicity with the evolution of gas-slurry flow pattern,whilst the heat transfer together with H_(2)O evaporation has little effect on overall absorption process.Three regions are firstly defined as Gas Inlet Region(GIR),Dominant Absorption Region(DAR)and Slurry Dispersed Region(SDR)from the bottom to top of scrubber.SO_(2) is mainly scrubbed in DAR,which provides much more intensive interaction between two phases compared to GIR or SDR.A better understanding of the desulfurization process is obtained from the fundamental relationship between transport phenomena and chemical reactions based upon the complicated hydrodynamics of gas-slurry two-phase flow,which should be useful for designing and optimizing the scrubber in coal-fired power unit.
文摘Selective flocculation is an idea separation method to separate ultrafine pyrite from coal. A number of selective flocculation separation tests under different conditions have been done and the results are very encouraging. The results also show that desulfurization and deashing can be finished simultaneously in selective fIocculation process. It is an advanced coal desulfurization process.
文摘The Beijing Research lnstitute of Coal Chemistry (BRICC) is developing the SMOVEN process for hot gas desulfurization. The SMOVEN process features sulfidation in an entrained bed,regeneration in a low velocity fluid bed or a moving bed with oxygen and sorbent circuIation con-trolled by gas stream. A series of tests on the bench scale unit and the continuous process devel-opment unit were carried out. The regenerable metal oxide sorbents were adopted for the sulfur-related components removing from coal gas at the temperature of 550-650℃. A fluidized bed gasifier of 100 mm (id) generated coal gas for tests. The principle of SMOVEN process has been positively verified.
基金Sponsored by the New Century Distinguished Experts Supporting Program (Grant No 2005601310)
文摘An anaerobic expanding-bed reactor was adopted to investigate the feasibility of an innovative integrated process of simultaneous desulfurization and denitrification (SDD) for high strength wastewater. In the reactor, heterotrophic bacteria (including sulfate reducing bacterium and denitrifying bacteria) and autotrophic bacteria (including Thiobacillus denitrificans) cooperated together by incubating and enriching functional bacteria on different carriers in the anaerobic activated sludge. Synthetic wastewater with high concentrations of sulfate and nitrate was employed. The experimental results showed that the removal efficiency of sulfate and nitrate was above 85%, elemental sulfur was observed while nitrate was absent in effluent. The balance of sulfur, nitrogen and electron was discussed respectively, which indicated that the integrated SDD process could be actualized. These results might provide a guidance to further investigate the key factors affecting the integrated SDD process and to improve the efficiency of desulfurization and denitrification in wastewater treatment.
基金Supported by Young Teachers Scientific Research Foundation Project of Sichuan University(2014SCU11020)National Key Research Project(2017YFB0307504)Sichuan Science and Technology Planning Project(2019YFH0149).
文摘Phosphogypsum(PG) desulfurization slag is a calcium-rich residue from reductive decomposition of PG using sulfur as the reductant. We proposed a technology of preparation light calcium carbonate with PG desulfurization slag, which mainly contains two steps: leaching and carbonizing. In this work, we concentrated on the former, in which ammonium chloride aqueous solution was utilized as leaching agent to extract calcium from the slag, and conducted thermodynamics and kinetics study on it. Fact Sage software was employed to do thermodynamic and phase equilibrium diagram calculations. The influence of leaching conditions including agitation speed, initial concentration of leaching solution, reaction temperature, and liquid/solid ratio on the calcium leaching rate was discussed in detail by means of experiment optimal design. A kinetic model developed from the shrinking core model was given to describe the leaching process. The apparent kinetic activation energy(Ea) of the leaching reaction was calculated to be 10.58 kJ·mol^-1.
基金financially supported by research grant from Sinopec(Fund No.118016-8)。
文摘The reactive adsorption behavior of thiophene on the reduced Ni/ZnO sample was investigated by a combination of theoretical and experimental study.It is widely accepted that Ni is responsible for the sulfur-removal of thiophene to release S-free hydrocarbons.Such surface reaction was simulated by DFT method.It is demonstrated that thiophene is mainly adsorbed as p-complexation mode over metallic Ni.During desulfurization,the Se Ni bond is formed and the Ce S bond is thus split without pre-hydrogenation,resulting in the formation of Ni_(3)S_(2)phase and S-free C4 olefin which can be further saturated in the presence of H_(2).The S-transfer between Ni_(3)S_(2)and ZnO was monitored by in-situ XRD and STEM with EDS mapping.Two essential features were identified for efficient S-transfer,namely,1)the H_(2)atmosphere,and 2)the two phases are presented with close contact.Based on the acquired information,a general scenario of sulfur trail has been proposed for the desulfurization of thiophene on Ni/ZnO.
文摘脱硫过程是具有高度动态非线性和较大延迟时间的复杂工业过程,为了解决烟气脱硫过程的建模问题,设计了注意力机制下的深度长短期记忆(attention mechanism-based long short-term memory,AttLSTM)网络,并基于该网络设计自动编码器,完成脱硫过程异常点的检测。该文首次提出使用AttLSTM网络自编码器对脱硫过程进行离群点检测,并且该网络模型同样首次应用于脱硫过程的辨识任务中。从更深的意义上讲,该文尝试使用深度学习模型对复杂系统进行辨识,所建立的AttLSTM网络之前未出现在系统辨识领域,该网络的出现可以丰富辨识模型的选择,同时为人工智能技术在系统辨识领域和控制领域的应用与推广提供参考。实验结果表明,相比于之前文献出现的脱硫过程建模方法,所提方法在不同性能指标上均具有更好的表现,由此可以证明深度AttLSTM网络在脱硫场景下的有效性。