A periodic packing mode of trickle-bed reactor (TBR) for the gas limited reaction was proposed. Hy-drogenation of 2-ethylanthraquinone over Pd/Al2O3 in a laboratory-scale TBR was taken as a test reaction for determini...A periodic packing mode of trickle-bed reactor (TBR) for the gas limited reaction was proposed. Hy-drogenation of 2-ethylanthraquinone over Pd/Al2O3 in a laboratory-scale TBR was taken as a test reaction for determining whether the periodic packing mode is advantageous. The effects of operating conditions and packing type on TBR performance were experimentally examined to demonstrate the cause-effect relationships. A mathe-matic model of TBR considering axial dispersion and fractional wetting was developed to quantitatively illuminate the reason of performance enhancement.展开更多
In this work,a trickle-bed reactor coupled with catalyst pellet model is employed to understand the effects of the temperature and catalyst pellet structures on the reaction-diffusion behaviors in gas oil hydrodesulfu...In this work,a trickle-bed reactor coupled with catalyst pellet model is employed to understand the effects of the temperature and catalyst pellet structures on the reaction-diffusion behaviors in gas oil hydrodesulfurization(HDS).The non-isothermal reactor model is determined to be reasonable due to non-negligible temperature variation caused by the reaction heat.The reaction rate along the reactor is mainly dominated by the temperature,and the sulfur concentration gradient in the catalyst pellet decreases gradually along the reactor,leading to the increased internal effectiveness factor.For the fixed catalyst bed volume,there exists a compromise between the catalyst reaction rate and effectiveness factor.Under commonly studied catalyst pellet size of 0.8-3 mm and porosity of 0.4-0.8,an optimization of the temperature and catalyst pellet structures is carried out,and the optimized outlet sulfur content decreases to 7.6 wppm better than the commercial level at 0.96 mm of the catalyst pellet size and 0.40 of the catalyst porosity.展开更多
Hydrodesulfurization(HDS) of sour crude oil is an effective way to address the corrosion problems in refineries and is an economic way to process sour crude oil in an existing refinery built for sweet oil.Siberian cru...Hydrodesulfurization(HDS) of sour crude oil is an effective way to address the corrosion problems in refineries and is an economic way to process sour crude oil in an existing refinery built for sweet oil.Siberian crude oil transported through the Russia-China pipeline could be greatly sweetened and could be refined directly in local refinery designed for Daqing crude oil after the effective HDS treatment.In this study,the HDS of Siberian crude oil was carried out in a continuous flow isothermal trickle-bed reactor over Ni-Mo/γ-Al_2 O_(3).The effects of temperature,pressure and LHSV were investigated in the ranges of 320-360℃,3-5 MPa and 0.5-2 h^(-1),keeping constant hydrogen to oil ratio at 600 L·L^(-1).The HDS conversion could be up to 92.89% at the temperature of 360℃, pressure of 5 MPa,and LHSV of 0.5 h^(-1), which is sufficient for local refineries(>84%).A three phase heterogeneous model was established to analyze the performance of the trickle-bed reactor based on the two-film theory using Langmuir-Hinshelwood mechanism.The order of sulfur component is estimated as 1.28,and the order of hydrogen is 0.39.By simulating the reactor using the established model,the concentration of H_(2), H_(2) S and sulfur along the catalyst bed is discussed.The model is significantly useful for industrial application with respect to reactor analysis,optimization and reactor design,and can provide further insight of the HDS of Siberian crude oil.展开更多
In this study, catalytic wet air oxidation of wastewater that contains organic matter (phenol) is investigated in a laboratory scale trickle-bed reactor. The aim of this project is to determine the optimum operating c...In this study, catalytic wet air oxidation of wastewater that contains organic matter (phenol) is investigated in a laboratory scale trickle-bed reactor. The aim of this project is to determine the optimum operating conditions for the reaction of phenol in the wastewater with oxygen using a catalyst. For this purpose, the effects of temperature, gas flow rate, liquid space velocity and initial concentration of phenol on the conversion of phenol at constant pressure and the effect of pressure on the conversion of phenol at constant temperature are investigated. An industrial copper chromite catalyst was used in the experimental studies. It is seen from the experimental results, conversion of phenol increases with increasing temperature, pressure, gas flow rate and liquid space velocity;and also, it is seen that conversion of phenol decreases with increasing initial concentration of phenol. The conversion of phenol reaches at 130?C and 4 bar to 40%. It was also found that, 3 ppm copper amount was determined from the exit stream of the reactor. This result shows that cupper placed in the structure of the catalyst, mixes with the liquid stream during the reaction.展开更多
Batch to batch temperature control of a semi-batch chemical reactor with heating/cooling system was discussed in this study. Without extensive modeling investigations, a two-dimensional(2D) general predictive iterativ...Batch to batch temperature control of a semi-batch chemical reactor with heating/cooling system was discussed in this study. Without extensive modeling investigations, a two-dimensional(2D) general predictive iterative learning control(2D-MGPILC) strategy based on the multi-model with time-varying weights was introduced for optimizing the tracking performance of desired temperature profile. This strategy was modeled based on an iterative learning control(ILC) algorithm for a 2D system and designed in the generalized predictive control(GPC) framework. Firstly, a multi-model structure with time-varying weights was developed to describe the complex operation of a general semi-batch reactor. Secondly, the 2 D-MGPILC algorithm was proposed to optimize simultaneously the dynamic performance along the time and batch axes. Finally, simulation for the controller design of a semi-batch reactor with multiple reactions was involved to demonstrate that the satisfactory performance could be achieved despite of the repetitive or non-repetitive disturbances.展开更多
Catalytic ozonation technology has attracted copious attention in water purification owing to its favorable oxidative degradation of pollutants and mitigation of membrane fouling capacity.However,its extensive industr...Catalytic ozonation technology has attracted copious attention in water purification owing to its favorable oxidative degradation of pollutants and mitigation of membrane fouling capacity.However,its extensive industrial application has been restricted by the low ozone utilization and limited mass transfer of the short-lived radical species.Interlayer space-confined catalysis has been theoretically proven to be a viable strategy for achieving high catalytic efficiency.Here,a two-dimensional MnO_(2)-incorporated ceramic membrane with tunable interspacing,which was obtained via the intercalation of a carbon nanotube,was designed as a catalytic ozonation membrane reactor for degrading methylene blue.Benefiting from the abundant catalytic active sites on the surface of two-dimensional MnO_(2) as well as the ultralow mass transfer resistance of fluids due to the nanolayer confinement,an excellent mineralization effect,i.e.,1.2 mg O_(3)(aq)mg^(-1) TOC removal(a total organic carbon removal rate of 71.5%),was achieved within a hydraulic retention time of 0.045 s of pollutant degradation.Further,the effects of hydraulic retention time and interlayer spacing on methylene blue removal were investigated.Moreover,the mechanism of the catalytic ozonation employing catalytic ozonation membrane was proposed based on the contribution of the Mn(III/IV)redox pair to electron transfer to generate the reactive oxygen species.This innovative twodimensional confinement catalytic ozonation membrane could act as a nanoreactor and separator to efficiently oxidize organic pollutants and enhance the control of membrane fouling during water purification.展开更多
Enantioselective hydrogenation of ethyl 2-oxo-4-phenylbutyrate to ethyl （R）-2-hydroxy-4-phenyl- bu- tyrate on Pt/γ-Al2O3 modified by 10,11-dihydrocinchonidine was studied by investigating the influences of the amou...Enantioselective hydrogenation of ethyl 2-oxo-4-phenylbutyrate to ethyl （R）-2-hydroxy-4-phenyl- bu- tyrate on Pt/γ-Al2O3 modified by 10,11-dihydrocinchonidine was studied by investigating the influences of the amount of modifier, initial concentration of reactant, pressure and temperature on conversion and enantiometric excess in a stirred autoclave and the effects of the liquid velocity, gas velocity, modifier concentration and various catalytic beds in a trickle-bed reactor. The maximum optical yields were about 50% and 60% in the two types of reactors, respectively. It was assumed that the total hydrogenation rate included the reaction rates over the unmodified and modified active sites on platinum surface and a kinetic model, which fitted the experimental data well in autoclave, was obtained. A simplified plug-flow model was proposed to describe the bed average efficiency of trickle-bed reactor.展开更多
In recent years,nanostructured photocatalysts have become the research focus due to their immense potential application in environmental purification and energy conversion.The photocatalytic performance of photocataly...In recent years,nanostructured photocatalysts have become the research focus due to their immense potential application in environmental purification and energy conversion.The photocatalytic performance of photocatalysts is closely related to their synthesis methods.High-intensity ultrasound irradiation could provide a unique tool for fabrication of photocatalysts with novel nanostructures.Ultrasound induces acoustic cavitation which generates unique physicochemical conditions,e.g.,hot spot（5000℃）,high pressure of 100 MPa,fast rate of heat conduction（〉〉1×10^10℃·s^-1）.These unique physicochemical conditions allow for the synthesis of various nanostructured photocatalysts.This review summarized the recent development in fabrication of photocatalysts with special nanostructures and their applications.The typical sonochemical reactors and parameters in sonochemical synthesis are introduced and discussed.Sonochemically prepared structures including nano-/microspheres,one-dimensional（1D） nanorods,two-dimensional（2D） nanosheets（nanoflakes,nanosquares）,noble metal nanoparticle（NP）-deposited and element-doped photocatalysts are described and summarized.It is believed that sonication is a green methodology,and it holds greatpotential in the near future for nanostructured photocatalyst fabrication.展开更多
The hysteresis of gas-liquid mass transfer rate and the corresponding radial liquiddistribution in a trickle bed reactor are measured to provide evidence for the correlation between thesetwo behaviors.Experimental res...The hysteresis of gas-liquid mass transfer rate and the corresponding radial liquiddistribution in a trickle bed reactor are measured to provide evidence for the correlation between thesetwo behaviors.Experimental results indicate that the hysteresis of gas-liquid mass transfer originatesfrom the nonuniformity of the hydrodynamic state of gas-liquid flow and the radial maldistributionof local k<sub>gia</sub> corresponds very well to the radial maldistribution of liquid flow in the bed.The localliquid flow rate is also found to be nonuniform in the azimuthal direction.In view of maldistributedliquid flow even in the pulsing flow regime,the conventional plug flow model seems oversimplifiedfor describing the behavior of a trickle bed.展开更多
This paper developed a new clean continuous process for the hydrogenation of 3,5-dimethylpyridine(DPY)to 3,5-dimethylpiperidine(DPI)without solvent.A series of Ru/C catalysts were prepared by impregnation method,which...This paper developed a new clean continuous process for the hydrogenation of 3,5-dimethylpyridine(DPY)to 3,5-dimethylpiperidine(DPI)without solvent.A series of Ru/C catalysts were prepared by impregnation method,which were characterized by the BET,ICP,CO chemisorptions,XRD,SEM,EDS,TEM and TG.The effect of active species,loading,catalyst support,reaction temperature and pressure on the catalytic performance was investigated.The influence of internal and external diffusion in the trickle-bed reactor(TBR)was basically eliminated by adjusting the particle size and dosage of the Ru/C catalyst.The reaction performance of the hydrogenation of DPY to DPI in the TBR and kettle reactor(KR)was compared,and the superiority of the TBR process was analyzed.The results show that this new continuous process developed in this study is an efficient way to realize the hydrogenation of DPY to DPI,and has a good industrial application prospect.展开更多
基金the State Key Development Program for Basic Research of China (No. G2000048005) the SINOPEC (No.X503023).
文摘A periodic packing mode of trickle-bed reactor (TBR) for the gas limited reaction was proposed. Hy-drogenation of 2-ethylanthraquinone over Pd/Al2O3 in a laboratory-scale TBR was taken as a test reaction for determining whether the periodic packing mode is advantageous. The effects of operating conditions and packing type on TBR performance were experimentally examined to demonstrate the cause-effect relationships. A mathe-matic model of TBR considering axial dispersion and fractional wetting was developed to quantitatively illuminate the reason of performance enhancement.
基金supported by the National Key R&D Program of China(2018YFB0604500)the National Natural Science Foundation of China(21922803 and 21776077)+4 种基金the Shanghai Natural Science Foundation(17ZR1407300 and 17ZR1407500)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learningthe Shanghai Rising-Star Program(17QA1401200)the Open Project of SKLOCE(SKL-Che-15C03)the 111 Project of the Ministry of Education of China(B08021)。
文摘In this work,a trickle-bed reactor coupled with catalyst pellet model is employed to understand the effects of the temperature and catalyst pellet structures on the reaction-diffusion behaviors in gas oil hydrodesulfurization(HDS).The non-isothermal reactor model is determined to be reasonable due to non-negligible temperature variation caused by the reaction heat.The reaction rate along the reactor is mainly dominated by the temperature,and the sulfur concentration gradient in the catalyst pellet decreases gradually along the reactor,leading to the increased internal effectiveness factor.For the fixed catalyst bed volume,there exists a compromise between the catalyst reaction rate and effectiveness factor.Under commonly studied catalyst pellet size of 0.8-3 mm and porosity of 0.4-0.8,an optimization of the temperature and catalyst pellet structures is carried out,and the optimized outlet sulfur content decreases to 7.6 wppm better than the commercial level at 0.96 mm of the catalyst pellet size and 0.40 of the catalyst porosity.
文摘Hydrodesulfurization(HDS) of sour crude oil is an effective way to address the corrosion problems in refineries and is an economic way to process sour crude oil in an existing refinery built for sweet oil.Siberian crude oil transported through the Russia-China pipeline could be greatly sweetened and could be refined directly in local refinery designed for Daqing crude oil after the effective HDS treatment.In this study,the HDS of Siberian crude oil was carried out in a continuous flow isothermal trickle-bed reactor over Ni-Mo/γ-Al_2 O_(3).The effects of temperature,pressure and LHSV were investigated in the ranges of 320-360℃,3-5 MPa and 0.5-2 h^(-1),keeping constant hydrogen to oil ratio at 600 L·L^(-1).The HDS conversion could be up to 92.89% at the temperature of 360℃, pressure of 5 MPa,and LHSV of 0.5 h^(-1), which is sufficient for local refineries(>84%).A three phase heterogeneous model was established to analyze the performance of the trickle-bed reactor based on the two-film theory using Langmuir-Hinshelwood mechanism.The order of sulfur component is estimated as 1.28,and the order of hydrogen is 0.39.By simulating the reactor using the established model,the concentration of H_(2), H_(2) S and sulfur along the catalyst bed is discussed.The model is significantly useful for industrial application with respect to reactor analysis,optimization and reactor design,and can provide further insight of the HDS of Siberian crude oil.
文摘In this study, catalytic wet air oxidation of wastewater that contains organic matter (phenol) is investigated in a laboratory scale trickle-bed reactor. The aim of this project is to determine the optimum operating conditions for the reaction of phenol in the wastewater with oxygen using a catalyst. For this purpose, the effects of temperature, gas flow rate, liquid space velocity and initial concentration of phenol on the conversion of phenol at constant pressure and the effect of pressure on the conversion of phenol at constant temperature are investigated. An industrial copper chromite catalyst was used in the experimental studies. It is seen from the experimental results, conversion of phenol increases with increasing temperature, pressure, gas flow rate and liquid space velocity;and also, it is seen that conversion of phenol decreases with increasing initial concentration of phenol. The conversion of phenol reaches at 130?C and 4 bar to 40%. It was also found that, 3 ppm copper amount was determined from the exit stream of the reactor. This result shows that cupper placed in the structure of the catalyst, mixes with the liquid stream during the reaction.
基金Projects(61673205,21727818,61503180)supported by the National Natural Science Foundation of ChinaProject(2017YFB0307304)supported by National Key R&D Program of ChinaProject(BK20141461)supported by the Natural Science Foundation of Jiangsu Province,China
文摘Batch to batch temperature control of a semi-batch chemical reactor with heating/cooling system was discussed in this study. Without extensive modeling investigations, a two-dimensional(2D) general predictive iterative learning control(2D-MGPILC) strategy based on the multi-model with time-varying weights was introduced for optimizing the tracking performance of desired temperature profile. This strategy was modeled based on an iterative learning control(ILC) algorithm for a 2D system and designed in the generalized predictive control(GPC) framework. Firstly, a multi-model structure with time-varying weights was developed to describe the complex operation of a general semi-batch reactor. Secondly, the 2 D-MGPILC algorithm was proposed to optimize simultaneously the dynamic performance along the time and batch axes. Finally, simulation for the controller design of a semi-batch reactor with multiple reactions was involved to demonstrate that the satisfactory performance could be achieved despite of the repetitive or non-repetitive disturbances.
基金supported by the National Natural Science Foundation of China(Grant Nos.21838005 and 21676139)the Key Scientific Research and Development Projects of Jiangsu Province(Grant No.BE201800901)。
文摘Catalytic ozonation technology has attracted copious attention in water purification owing to its favorable oxidative degradation of pollutants and mitigation of membrane fouling capacity.However,its extensive industrial application has been restricted by the low ozone utilization and limited mass transfer of the short-lived radical species.Interlayer space-confined catalysis has been theoretically proven to be a viable strategy for achieving high catalytic efficiency.Here,a two-dimensional MnO_(2)-incorporated ceramic membrane with tunable interspacing,which was obtained via the intercalation of a carbon nanotube,was designed as a catalytic ozonation membrane reactor for degrading methylene blue.Benefiting from the abundant catalytic active sites on the surface of two-dimensional MnO_(2) as well as the ultralow mass transfer resistance of fluids due to the nanolayer confinement,an excellent mineralization effect,i.e.,1.2 mg O_(3)(aq)mg^(-1) TOC removal(a total organic carbon removal rate of 71.5%),was achieved within a hydraulic retention time of 0.045 s of pollutant degradation.Further,the effects of hydraulic retention time and interlayer spacing on methylene blue removal were investigated.Moreover,the mechanism of the catalytic ozonation employing catalytic ozonation membrane was proposed based on the contribution of the Mn(III/IV)redox pair to electron transfer to generate the reactive oxygen species.This innovative twodimensional confinement catalytic ozonation membrane could act as a nanoreactor and separator to efficiently oxidize organic pollutants and enhance the control of membrane fouling during water purification.
文摘Enantioselective hydrogenation of ethyl 2-oxo-4-phenylbutyrate to ethyl （R）-2-hydroxy-4-phenyl- bu- tyrate on Pt/γ-Al2O3 modified by 10,11-dihydrocinchonidine was studied by investigating the influences of the amount of modifier, initial concentration of reactant, pressure and temperature on conversion and enantiometric excess in a stirred autoclave and the effects of the liquid velocity, gas velocity, modifier concentration and various catalytic beds in a trickle-bed reactor. The maximum optical yields were about 50% and 60% in the two types of reactors, respectively. It was assumed that the total hydrogenation rate included the reaction rates over the unmodified and modified active sites on platinum surface and a kinetic model, which fitted the experimental data well in autoclave, was obtained. A simplified plug-flow model was proposed to describe the bed average efficiency of trickle-bed reactor.
基金financially supported by the National Natural Science Foundation of China (Nos.21567008 and 21263005)the Young Scientist Training Project of Jiangxi Province China (No.20122BCB23015)+2 种基金Jiangxi Province Natural Science Foundation (No.20133BAB21003)the Landing Project of Science and Technology of Colleges and Universities in Jiangxi Province (No.KJLD14046)Yuan Hang Gongcheng of Jiangxi Province (2014)
文摘In recent years,nanostructured photocatalysts have become the research focus due to their immense potential application in environmental purification and energy conversion.The photocatalytic performance of photocatalysts is closely related to their synthesis methods.High-intensity ultrasound irradiation could provide a unique tool for fabrication of photocatalysts with novel nanostructures.Ultrasound induces acoustic cavitation which generates unique physicochemical conditions,e.g.,hot spot（5000℃）,high pressure of 100 MPa,fast rate of heat conduction（〉〉1×10^10℃·s^-1）.These unique physicochemical conditions allow for the synthesis of various nanostructured photocatalysts.This review summarized the recent development in fabrication of photocatalysts with special nanostructures and their applications.The typical sonochemical reactors and parameters in sonochemical synthesis are introduced and discussed.Sonochemically prepared structures including nano-/microspheres,one-dimensional（1D） nanorods,two-dimensional（2D） nanosheets（nanoflakes,nanosquares）,noble metal nanoparticle（NP）-deposited and element-doped photocatalysts are described and summarized.It is believed that sonication is a green methodology,and it holds greatpotential in the near future for nanostructured photocatalyst fabrication.
基金Supported by the National Natural Science Foundation of China and SINOPEC
文摘The hysteresis of gas-liquid mass transfer rate and the corresponding radial liquiddistribution in a trickle bed reactor are measured to provide evidence for the correlation between thesetwo behaviors.Experimental results indicate that the hysteresis of gas-liquid mass transfer originatesfrom the nonuniformity of the hydrodynamic state of gas-liquid flow and the radial maldistributionof local k<sub>gia</sub> corresponds very well to the radial maldistribution of liquid flow in the bed.The localliquid flow rate is also found to be nonuniform in the azimuthal direction.In view of maldistributedliquid flow even in the pulsing flow regime,the conventional plug flow model seems oversimplifiedfor describing the behavior of a trickle bed.
基金supported by the National Natural Science Foun-dation of China(21536009)the Science and Technology Plan Projects of Shaanxi Province(2017ZDCXL-GY-10-03).
文摘This paper developed a new clean continuous process for the hydrogenation of 3,5-dimethylpyridine(DPY)to 3,5-dimethylpiperidine(DPI)without solvent.A series of Ru/C catalysts were prepared by impregnation method,which were characterized by the BET,ICP,CO chemisorptions,XRD,SEM,EDS,TEM and TG.The effect of active species,loading,catalyst support,reaction temperature and pressure on the catalytic performance was investigated.The influence of internal and external diffusion in the trickle-bed reactor(TBR)was basically eliminated by adjusting the particle size and dosage of the Ru/C catalyst.The reaction performance of the hydrogenation of DPY to DPI in the TBR and kettle reactor(KR)was compared,and the superiority of the TBR process was analyzed.The results show that this new continuous process developed in this study is an efficient way to realize the hydrogenation of DPY to DPI,and has a good industrial application prospect.
