The selective hydrogenation of polycyclic aromatic hydrocarbons(PAHs)from fluid catalytic cracking(FCC)slurry extract was conducted in a batch reactor over aγ-Al_(2)O_(3)-supported bimetallic Ni-W catalyst.For the Ni...The selective hydrogenation of polycyclic aromatic hydrocarbons(PAHs)from fluid catalytic cracking(FCC)slurry extract was conducted in a batch reactor over aγ-Al_(2)O_(3)-supported bimetallic Ni-W catalyst.For the Ni-W/γ-Al_(2)O_(3) catalyst,the experiment run was divided into three processes according to the reaction conditions used:(1)the absence of hydrogenation as both temperature and pressure increased;(2)the desulfurization of FCC slurry extract under a fixed pressure as the temperature increased;and(3)the selective hydrogenation of PAHs when both pressure and temperature remained constant.The hydrogen consumption could be accurately calculated from the Redlich–Kwong equation of state.The results for the removal of PAHs with hydrogenation displayed an excellent fit to the first-order kinetics.The apparent activation energy was determined to be 20.80 kJ/mol.展开更多
With the rapid development of modern industry,high-grade paving asphalt is massively required to meet the demands for modern transportation.As one of additives,natural asphalt is indispensable since it can improve the...With the rapid development of modern industry,high-grade paving asphalt is massively required to meet the demands for modern transportation.As one of additives,natural asphalt is indispensable since it can improve the performance of paving asphalt in all aspects.However,the application of non-renewable natural asphalt is increasingly restricted by its limited reserves.It is imperative to find alternative approaches to produce high-grade paving asphalt.Fluid catalytic cracking(FCC)slurry oil is an ideal soft component for producing paving asphalt due to its high content of aromatics and resins.However,its bad ageing resistance limits its application to only low-grade paving asphalt.In the present work,a novel approach for producing high-grade paving asphalt was investigated using chemically modified FCC slurry oil and deoiled asphalt(DOA).The FT-IR and NMR results showed that dehydrogenation and condensation reaction occurred during the ageing process.From a series of aliphatic alcohols and aldehydes,propanal was selected as a proper modifier to improve the ageing resistance of FCC slurry oil.The propanalmodified slurry oil possessed more substituted aromatic units and less aromatic hydrogen atoms than other modified slurry oils,thus showing better ageing resistance.With the increase of length of aliphatic chains in modifier,the modified slurry oil contained more and longer alkyl substituent group on aromatics.Compared with the cross-linked oil(slurry oil modified by cross-linking agent),modified slurry oil possessed similar ageing resistance but higher flowing ability.Also,the effect of operation conditions on the kinematic viscosity of modified slurry oil were investigated.Blended with modified slurry oil,the penetration ratio of asphalt product increased from 53.7 to 66.2,which met the standard of 70#paving asphalt.Both the microscopic observations and FT-IR results indicated that modification process effectively reduced the oxidation degree of asphalt product,thus increasing the ageing resistance.Consequently,with aid of this process,high-grade paving asphalt was readily produced from low value oil from downstream products of refinery,instead of the depleting natural asphalt.展开更多
Daqing FCC slurry was treated using mixed solvent containing N,N-dimethylformamide(extraction solvent)and n-paraffin(stripping-agent).The influence of solvent formulation(ratio of DMF/stripping-agent),temperature,time...Daqing FCC slurry was treated using mixed solvent containing N,N-dimethylformamide(extraction solvent)and n-paraffin(stripping-agent).The influence of solvent formulation(ratio of DMF/stripping-agent),temperature,time and solvent-oil ratio on yield and aromatics content of the extract oil were analyzed by a four-factor and three-level orthogonal experimental design.The polynomial regression models between the extract oil yield and aromatics content with the four factors were established.Response surface analysis showed that solvent formulation,temperature and solvent-oil ratio have significant effects on extraction result and there is an interaction between temperature and solvent-oil ratio on aromatics content,when the FCC slurry is extracted by mixed solvent.However,the extraction time has no significant effect.The optimal conditions for FCC slurry extraction covered:a solvent mixed ratio of 2.3,a temperature of 62.8℃,a solvent-oil ratio of 3.2,and a time of 35 min.The result of verification experiment was in good agreement with the prediction of the model.展开更多
The characteristics of the packing material under an alternating electric field are an important factor in the removal of FCCS particles.In this study,the electric field distribution of a separation unit consisting of...The characteristics of the packing material under an alternating electric field are an important factor in the removal of FCCS particles.In this study,the electric field distribution of a separation unit consisting of packed spheres under an alternating electric field is simulated,and the movement mechanism of catalyst particles is analysed.An"effective contact point"model is derived to predict the adsorption of filler contact points on catalyst particles under the alternating electric field,and the model is validated by simulations and experiments.The numerical calculation and experimental results indicate that the electrical properties of the filler spheres,the filler angleθ,and the frequency f of the alternating electric field affect the adsorption of catalyst particles.As the frequency of the electric field increases,the particle removal efficiency of the high-conductivity filler(silicon carbide)increases and then settles,and the separation efficiency of the low-conductivity filler(glass,zirconia)is not sensitive to the change in electric field frequency.展开更多
Mesoporous NiMoAl catalysts with boron phosphate(BPO4)modification were synthesized through the complete liquid-phase method.X-ray diffraction(XRD)analysis evidenced the presence of BPO4-AlOOH mixed support in these B...Mesoporous NiMoAl catalysts with boron phosphate(BPO4)modification were synthesized through the complete liquid-phase method.X-ray diffraction(XRD)analysis evidenced the presence of BPO4-AlOOH mixed support in these BPO4-modified NiMoAl samples.The total amount of acid sites declined,but the surface acidity was strengthened by adding BPO4 into the NiMoAl catalyst.It’s worth noting that the incorporation of BPO4 could increase the concentrations of Ni and Mo species on the catalyst surface and greatly improve the dispersion of(Ni)MoS2 active phases,as indicated by X-ray photoelectron spectroscopy(XPS)and transmission electron microscopy(TEM)measurements.The catalytic performance of these BPO_(4)-modified NiMoAl catalysts was investigated with the hydroprocessing of fluid catalytic cracking(FCC)slurry oil.The nitrogen-containing compounds removal from the oil was significantly enhanced with increasing the molar ratio of boron phosphate/aluminum.The NM-BPA(0.55)catalyst exhibited the best hydrodenitrogenation(HDN)activity,highlighting the significant impact of Mo sulfidation degree and the dispersion of active metals on HDN performance.The introduction of boron phosphate could also promote the hydrocracking activity of the NiMoAl catalyst,as demonstrated by SARA analysis and simulated distillation of liquid products.展开更多
Catalytic cracking is the main method to lighten heavy crude oil,this process can produce high quality oil products such as gasoline and diesel,but also produces a large amount of fluid catalytic cracking slurry(FCCS)...Catalytic cracking is the main method to lighten heavy crude oil,this process can produce high quality oil products such as gasoline and diesel,but also produces a large amount of fluid catalytic cracking slurry(FCCS).The catalyst particles in FCCS seriously restrict the secondary processing of FCCS and need to be removed,and the properties of Fccs is an important factor that affects the removal efficiency of the catalyst particles.Based on the"effective contact point"model proposed by the research group,this study further proposed the"electrostatic separation efficiency calculation"model.In this model,since Fccs has a uniform distribution of catalyst particles,the ratio of the number of catalyst particles can be expressed as the ratio of area to achieve the calculation of separation efficiency.Then the catalyst removal efficiency under different viscosity was analyzed,thus verifying the feasibility of this model.The effects of temperature and mass ratio of four components on the viscosity of FccS were investigated respectively,then the effects of temperature and four components'mass ratio on the electrostatic sep-aration can be directly converted into the effect of viscosity on the electrostatic separation efficiency.All the results show the electrostatic separation efficiency decreases with increasing viscosity,and the best separationtemperatureis120℃.展开更多
基金financially supported by the Natural Science Foundation of Jiangsu Province (Grant number:BK20140260)the Joint Project of Industry-UniversityResearch of Jiangsu Province (Grant number:BY2018158 and BY2021590)+1 种基金the CNPC-CZU Innovation Alliance,the Jiangsu Province Key Laboratory of Fine Petrochemical Engineering (Grant number:KF2302)the State Key Laboratory of Heavy Oil Processing。
文摘The selective hydrogenation of polycyclic aromatic hydrocarbons(PAHs)from fluid catalytic cracking(FCC)slurry extract was conducted in a batch reactor over aγ-Al_(2)O_(3)-supported bimetallic Ni-W catalyst.For the Ni-W/γ-Al_(2)O_(3) catalyst,the experiment run was divided into three processes according to the reaction conditions used:(1)the absence of hydrogenation as both temperature and pressure increased;(2)the desulfurization of FCC slurry extract under a fixed pressure as the temperature increased;and(3)the selective hydrogenation of PAHs when both pressure and temperature remained constant.The hydrogen consumption could be accurately calculated from the Redlich–Kwong equation of state.The results for the removal of PAHs with hydrogenation displayed an excellent fit to the first-order kinetics.The apparent activation energy was determined to be 20.80 kJ/mol.
基金the financial support by Sinopec Innovation Foundation(118009-3)。
文摘With the rapid development of modern industry,high-grade paving asphalt is massively required to meet the demands for modern transportation.As one of additives,natural asphalt is indispensable since it can improve the performance of paving asphalt in all aspects.However,the application of non-renewable natural asphalt is increasingly restricted by its limited reserves.It is imperative to find alternative approaches to produce high-grade paving asphalt.Fluid catalytic cracking(FCC)slurry oil is an ideal soft component for producing paving asphalt due to its high content of aromatics and resins.However,its bad ageing resistance limits its application to only low-grade paving asphalt.In the present work,a novel approach for producing high-grade paving asphalt was investigated using chemically modified FCC slurry oil and deoiled asphalt(DOA).The FT-IR and NMR results showed that dehydrogenation and condensation reaction occurred during the ageing process.From a series of aliphatic alcohols and aldehydes,propanal was selected as a proper modifier to improve the ageing resistance of FCC slurry oil.The propanalmodified slurry oil possessed more substituted aromatic units and less aromatic hydrogen atoms than other modified slurry oils,thus showing better ageing resistance.With the increase of length of aliphatic chains in modifier,the modified slurry oil contained more and longer alkyl substituent group on aromatics.Compared with the cross-linked oil(slurry oil modified by cross-linking agent),modified slurry oil possessed similar ageing resistance but higher flowing ability.Also,the effect of operation conditions on the kinematic viscosity of modified slurry oil were investigated.Blended with modified slurry oil,the penetration ratio of asphalt product increased from 53.7 to 66.2,which met the standard of 70#paving asphalt.Both the microscopic observations and FT-IR results indicated that modification process effectively reduced the oxidation degree of asphalt product,thus increasing the ageing resistance.Consequently,with aid of this process,high-grade paving asphalt was readily produced from low value oil from downstream products of refinery,instead of the depleting natural asphalt.
文摘Daqing FCC slurry was treated using mixed solvent containing N,N-dimethylformamide(extraction solvent)and n-paraffin(stripping-agent).The influence of solvent formulation(ratio of DMF/stripping-agent),temperature,time and solvent-oil ratio on yield and aromatics content of the extract oil were analyzed by a four-factor and three-level orthogonal experimental design.The polynomial regression models between the extract oil yield and aromatics content with the four factors were established.Response surface analysis showed that solvent formulation,temperature and solvent-oil ratio have significant effects on extraction result and there is an interaction between temperature and solvent-oil ratio on aromatics content,when the FCC slurry is extracted by mixed solvent.However,the extraction time has no significant effect.The optimal conditions for FCC slurry extraction covered:a solvent mixed ratio of 2.3,a temperature of 62.8℃,a solvent-oil ratio of 3.2,and a time of 35 min.The result of verification experiment was in good agreement with the prediction of the model.
基金supported by the Natural Scienceof Shandong Province,China(ZR2019MEE033)。
文摘The characteristics of the packing material under an alternating electric field are an important factor in the removal of FCCS particles.In this study,the electric field distribution of a separation unit consisting of packed spheres under an alternating electric field is simulated,and the movement mechanism of catalyst particles is analysed.An"effective contact point"model is derived to predict the adsorption of filler contact points on catalyst particles under the alternating electric field,and the model is validated by simulations and experiments.The numerical calculation and experimental results indicate that the electrical properties of the filler spheres,the filler angleθ,and the frequency f of the alternating electric field affect the adsorption of catalyst particles.As the frequency of the electric field increases,the particle removal efficiency of the high-conductivity filler(silicon carbide)increases and then settles,and the separation efficiency of the low-conductivity filler(glass,zirconia)is not sensitive to the change in electric field frequency.
基金This work was supported by the National Natural Science Foundation of China(21808155)the National Key R&D Program of China(2018YFB0604600-01).
文摘Mesoporous NiMoAl catalysts with boron phosphate(BPO4)modification were synthesized through the complete liquid-phase method.X-ray diffraction(XRD)analysis evidenced the presence of BPO4-AlOOH mixed support in these BPO4-modified NiMoAl samples.The total amount of acid sites declined,but the surface acidity was strengthened by adding BPO4 into the NiMoAl catalyst.It’s worth noting that the incorporation of BPO4 could increase the concentrations of Ni and Mo species on the catalyst surface and greatly improve the dispersion of(Ni)MoS2 active phases,as indicated by X-ray photoelectron spectroscopy(XPS)and transmission electron microscopy(TEM)measurements.The catalytic performance of these BPO_(4)-modified NiMoAl catalysts was investigated with the hydroprocessing of fluid catalytic cracking(FCC)slurry oil.The nitrogen-containing compounds removal from the oil was significantly enhanced with increasing the molar ratio of boron phosphate/aluminum.The NM-BPA(0.55)catalyst exhibited the best hydrodenitrogenation(HDN)activity,highlighting the significant impact of Mo sulfidation degree and the dispersion of active metals on HDN performance.The introduction of boron phosphate could also promote the hydrocracking activity of the NiMoAl catalyst,as demonstrated by SARA analysis and simulated distillation of liquid products.
基金supported by the[Natural Science Foundation Project of Shandong Province#1]under Grant[ZR2019MEE033][Fundamental Research Funds for the central Universities#2]under Grant[19CX02035A].
文摘Catalytic cracking is the main method to lighten heavy crude oil,this process can produce high quality oil products such as gasoline and diesel,but also produces a large amount of fluid catalytic cracking slurry(FCCS).The catalyst particles in FCCS seriously restrict the secondary processing of FCCS and need to be removed,and the properties of Fccs is an important factor that affects the removal efficiency of the catalyst particles.Based on the"effective contact point"model proposed by the research group,this study further proposed the"electrostatic separation efficiency calculation"model.In this model,since Fccs has a uniform distribution of catalyst particles,the ratio of the number of catalyst particles can be expressed as the ratio of area to achieve the calculation of separation efficiency.Then the catalyst removal efficiency under different viscosity was analyzed,thus verifying the feasibility of this model.The effects of temperature and mass ratio of four components on the viscosity of FccS were investigated respectively,then the effects of temperature and four components'mass ratio on the electrostatic sep-aration can be directly converted into the effect of viscosity on the electrostatic separation efficiency.All the results show the electrostatic separation efficiency decreases with increasing viscosity,and the best separationtemperatureis120℃.