A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO_(2) photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the ph...A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO_(2) photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the photon utilization efficiency for succinonitrile synthesis at room temperature.The space time yield of succinonitrile reached 55.59μmol/(g·h)over hydrophobic TiO_(2) catalyst,which was much higher than that of pristine TiO_(2)(4.23μmol/(g·h)).Mechanistic studies revealed that the hydrophobic modification of TiO_(2) promoted the separation and transfer of photogenerated carriers,as well as suppressed their recombination.Hydrophobic TiO_(2) also enhanced the adsorption of−CH3 of acetonitrile,thus facilitating the activation of C−H bond and the utilization efficiency of photocarriers.展开更多
The oxidative coupling of methane （OCM） to ethylene over a perovskite titanate catalyst in a fixed bed reactor was studied experimentally and numerically. The two-dimensional steady state model accounted for separat...The oxidative coupling of methane （OCM） to ethylene over a perovskite titanate catalyst in a fixed bed reactor was studied experimentally and numerically. The two-dimensional steady state model accounted for separate energy equations for the gas and solid phases coupled with an experimental kinetic model. A lumped kinetic model containing four main species CH4, O2, COx （CO2, CO）, and C2 （C2H4 and C2H6） was used with a plug flow reactor model as well. The results from the model agreed with the experimental data. The model was used to analyze the influence of temperature and feed gas composition on the conversion and selectivity of the reactor performance. The analytical results indicate that the conversion decreases, whereas, C2 selectivity increases by increasing gas hourly space velocity （GHSV） and the methane conversion also decreases by increasing the methane to oxygen ratio.展开更多
The study of scale up for the oxidative coupling of methane （OCM） has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 （W-Mn/SiO2） catalyst. The effects of reaction ...The study of scale up for the oxidative coupling of methane （OCM） has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 （W-Mn/SiO2） catalyst. The effects of reaction conditions were investigated in detail. The results showed that, with increasing reaction temperature, the gas-phase reaction was enhanced and a significant amount of methane was converted into COx; with the CH4/O2 molar ratio of 5, the highest C2 （ethylene and ethane） yield of 25% was achieved; the presence of steam （as diluent） had a positive effect on the C2 selectivity and yield. Under lower methane gaseous hourly space velocity （GHSV）, higher selectivity and yield of C2 were obtained as the result of the decrease of released heat energy. In 100 h reaction time, the C2 selectivity of 66%-61% and C2 yield of 24.2%-25.4% were achieved by a single pass without any significant loss in catalytic performance.展开更多
In this study,a multi-physics and multi-scale coupling program,Fluent/KMC-sub/NDK,was developed based on the user-defined functions(UDF)of Fluent,in which the KMC-sub-code is a sub-channel thermal-hydraulic code and t...In this study,a multi-physics and multi-scale coupling program,Fluent/KMC-sub/NDK,was developed based on the user-defined functions(UDF)of Fluent,in which the KMC-sub-code is a sub-channel thermal-hydraulic code and the NDK code is a neutron diffusion code.The coupling program framework adopts the"master-slave"mode,in which Fluent is the master program while NDK and KMC-sub are coupled internally and compiled into the dynamic link library(DLL)as slave codes.The domain decomposition method was adopted,in which the reactor core was simulated by NDK and KMC-sub,while the rest of the primary loop was simulated using Fluent.A simulation of the reactor shutdown process of M2LFR-1000 was carried out using the coupling program,and the code-to-code verification was performed with ATHLET,demonstrating a good agreement,with absolute deviation was smaller than 0.2%.The results show an obvious thermal stratification phenomenon during the shutdown process,which occurs 10 s after shutdown,and the change in thermal stratification phenomena is also captured by the coupling program.At the same time,the change in the neutron flux density distribution of the reactor was also obtained.展开更多
In the core of a molten salt fast reactor(MSFR),heavy metal fuel and fission products can be dissolved in a molten fluoride salt to form a eutectic mixture that acts as both fuel and coolant.Fission energy is released...In the core of a molten salt fast reactor(MSFR),heavy metal fuel and fission products can be dissolved in a molten fluoride salt to form a eutectic mixture that acts as both fuel and coolant.Fission energy is released from the fuel salt and transferred to the second loop by fuel salt circulation.Therefore,the MSFR is characterized by strong interaction between the neutronics and the thermal hydraulics.Moreover,recirculation flow occurs,and nuclear heat is accumulated near the fertile blanket,which significantly affects both the flow and the temperature fields in the core.In this work,to further optimize the conceptual geometric design of the MSFR,three geometries of the core and fertile blanket are proposed,and the thermal-hydraulic characteristics,including the three-dimensional flow and temperature fields of the fuel and fertile salts,are simulated and analyzed using a coupling scheme between the open source codes OpenMC and OpenFOAM.The numerical results indicate that a flatter core temperature distribution can be obtained and the hot spot and flow stagnation zones that appear in the upper and lower parts of the core center near the reflector can be eliminated by curving both the top and bottom walls of the core.Moreover,eight cooling loops with a total flow rate of0.0555 m3 s-1 ensur an acceptable temperature distribusure an acceptable temperature distribution in the fertile blanket.展开更多
A dual-bed reactor was constructed comprising of a 5%Na2WO4-2%Mn/SiO2 particle catalyst and a 4%Ce-5%Na2WO4-2%Mn/SiO2 /cordierite monolithic catalyst.The reaction performance of the oxidative coupling of methane （OCM...A dual-bed reactor was constructed comprising of a 5%Na2WO4-2%Mn/SiO2 particle catalyst and a 4%Ce-5%Na2WO4-2%Mn/SiO2 /cordierite monolithic catalyst.The reaction performance of the oxidative coupling of methane （OCM） over the dual-bed reactor system was evaluated.The effects of the bed height and operation mode,as well as the reaction parameters such as reaction temperature,CH4/O2 ratio and flowrate of feed gas,on the catalytic performance were investigated.The results indicated that the suggested dual-bed reactor exhibited a good performance for the OCM reaction when the feed gases firstly passed through the particle catalyst bed and then to the monolithic catalyst bed.A CH4 conversion of 38.2% and a C2H4 selectivity of 43.3% could be obtained using the dual-bed reactor with a particle catalyst bed height of 10 mm and a monolithic catalyst bed height of 50 mm.Both the CH4 conversion and C2H4 selectivity have increased by 2.5% and 12.8%,respectively,as compared with the 5%Na2WO4-2%Mn/SiO2 particle catalyst in a conventional single-bed reactor and by 12.9% and 23.0%,respectively,as compared with the 4%Ce-5%Na2WO4-2%Mn/SiO2 /cordierite monolithic catalyst in a single-bed reactor.The catalytic performance of the OCM in the dual-bed reactor system has been improved remarkably.展开更多
Performance of the oxidative coupling of methane in fluidized-bed reactor was experimentally investigated using Mn-Na2WO4/SiO2,La2O3/CaO and La2O3-SrO/CaO catalysts.These catalysts were found to be stable,especially M...Performance of the oxidative coupling of methane in fluidized-bed reactor was experimentally investigated using Mn-Na2WO4/SiO2,La2O3/CaO and La2O3-SrO/CaO catalysts.These catalysts were found to be stable,especially Mn-Na2WO4/SiO2 catalyst.The effect of sodium content of this catalyst was analyzed and the challenge of catalyst agglomeration was addressed using proper catalyst composition of 2%Mn2.2%Na2WO4/SiO2.For other two catalysts,the effect of Lanthanum-Strontium content was analyzed and 10%La2O 3-20%SrO/CaO catalyst was found to provide higher ethylene yield than La2O3/CaO catalyst.Furthermore,the effect of operating parameters such as temperature and methane to oxygen ratio were also reviewed.The highest ethylene and ethane （C2） yield was achieved with the lowest methane to oxygen ratio around 2.40.5% selectivity to ethylene and ethane and 41% methane conversion were achieved over La2O3-SrO/CaO catalyst while over Mn-Na2WO4 /SiO2 catalyst,40% and 48% were recorded,respectively.Moreover,the consecutive effects of nitrogen dilution,ethylene to ethane production ratio and other performance indicators on the down-stream process units were qualitatively discussed and Mn-Na2WO4/SiO2 catalyst showed a better performance in the reactor and process scale analysis.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
The bifurcation behavior of the CO coupling reactor was examined based on the one-dimensional pseudo homogeneous axial dispersion dynamic model. The method of finite difference was used for solving the boundary value ...The bifurcation behavior of the CO coupling reactor was examined based on the one-dimensional pseudo homogeneous axial dispersion dynamic model. The method of finite difference was used for solving the boundary value problem; the continuation technique and the direct method were applied to determine the bifurcation diagram. The effects of dimensionless adiabatic temperature rise, Damkohler number, activation energy, heat transfer coefficient and feed ratio on the bifurcation behavior were investigated. It was shown that there existed static bifurcation and the oscillations did not occur in the reactor. The result also revealed that the reactor exhibited at most 1-3-1 multiplicity patterns within the range of practical possible parameters and the measures, such as weakening the axial dispersion of reactor, enhancing heat transfer, decreasing the concentration of ethyl nitrite, were efficient for avoiding the possible risk of multiple steady states.展开更多
A three-dimensional geometric model was set up for the oxidative coupling of methane(OCM) fixed bed reactor loaded with Na_3PO_4-Mn/SiO_2/cordierite monolithic catalyst,and an improved Stansch kinetic model was establ...A three-dimensional geometric model was set up for the oxidative coupling of methane(OCM) fixed bed reactor loaded with Na_3PO_4-Mn/SiO_2/cordierite monolithic catalyst,and an improved Stansch kinetic model was established to calculate the OCM reactions using the computational fluid dynamics method and Fluent software.The simulation conditions were completely the same with the experimental conditions that the volume velocity of the reactant is 80 ml·min^(-1) under standard state,the CH_4/O_2 ratio is 3 and the temperature and pressure is800 ℃ and 1 atm,respectively.The contour of the characteristic parameters in the catalyst bed was analyzed,such as the species mass fractions,temperature,the heat flux on side wall surface,pressure,fluid density and velocity.The results showed that the calculated values matched well with the experimental values on the conversion of CH4 and the selectivity of products(C_2H_6,C_2H_4,CO,CO_2 and H_2) in the reactor outlet with an error range of±4%.The mass fractions of CH_4 and O_2 decreased from 0.600 and 0.400 at the catalyst bed inlet to 0.445 and0.120 at the outlet,where the mass fractions of C_2H_6,C_2H_4,CO and CO_2 were 0.0245,0.0460,0.0537 and 0.116,respectively.Due to the existence of laminar boundary layer,the mass fraction contours of each species bent upwards in the vicinity of the boundary layer.The volume of OCM reaction was changing with the proceeding of reaction,and the total moles of products were greater than reactants.The flow field in the catalyst bed maintained constant temperature and pressure.The fluid density decreased gradually from 2.28 kg·m^(-3) at the inlet of the catalyst bed to 2.18 kg·m^(-3) at the outlet of the catalyst bed,while the average velocity magnitude increased from 0.108 m·s-1 to 0.120 m·s^(-1).展开更多
Coupling adsorption and in-situ Fenton-like oxidation process was developed for Methylene blue(MB) using refined iron-containing lowgrade attapulgite(ATP) clay, and the removal mechanism was investigated. The MB was i...Coupling adsorption and in-situ Fenton-like oxidation process was developed for Methylene blue(MB) using refined iron-containing lowgrade attapulgite(ATP) clay, and the removal mechanism was investigated. The MB was initially adsorbed on the porous ATPs, and then the enriched MB was removed by the H2O2-assisted Fenton-like oxidation with the iron-containing ATP catalyst. Under optimal conditions, the ATP powder exhibits the maximum removal efficiency of 100% with negligible iron leaching(1.5 mg L^(-1)) and no sludge formation. Furthermore,polysulfone/ATP(PSF/ATP) pellets were fabricated through a water-induced phase separation process to construct a fixed-bed reactor(FBR) for continuous contaminant removal. For the first cycle, the maximum adsorption capacity was 15.5 L with an outlet MB concentration of1.973 mg L-1(< 2 mg L^(-1), GB4287-2012) using the PSF/ATP pellets containing 50.0 g of ATP powders, and the maximum Fenton-like oxidation capacity was 35.5 L with the outlet concentration of 0.831 mg L^(-1). After five cycles, the total treated volume of the MB solution was ca. 255 L, and the efficiency remained above 99%. After 10 h of continuous treatment towards practical resin industrial wastewater, the chemical oxygen demand(COD) removal efficiency was still measured at 83.05%, costing 0.398 $ m^(-3). These results demonstrate the practical applicability of iron-containing low-grade ATP clay for textile water treatment.展开更多
A three-dimensional geometric model of the oxidative coupling of methane （OCM） packed-bed reactor loaded with Na2WO4-Mn/SiO2 partic- ulate catalyst was set up, and an improved Stansch kinetic model was established t...A three-dimensional geometric model of the oxidative coupling of methane （OCM） packed-bed reactor loaded with Na2WO4-Mn/SiO2 partic- ulate catalyst was set up, and an improved Stansch kinetic model was established to calculate the OCM reactions using the computational fluid dynamics method and Fluent software. The simulation conditions were completely the same with the experimental conditions that the volume velocity of the reactant was 80 mL/min under standard state, the ratio of CH4/O2 was 3, the temperature and pressure were 800 ℃ and 1 atm, respectively. The contour of the characteristics parameters in the catalyst bed was analyzed, such as the species mass fractions, temperature, the heat flux on side wall surface, pressure, fluid density and velocity. The results showed that the calculated values matched well with the experimental values on the conversion of CH4 and the selectivity to products （C2H6, C2H4, CO2, CO） in the reactor outlet with an error range of 4-2%. The mass fractions of CH4 and O2 decreased from 0.6 and 0.4 in the catalyst bed inlet to 0.436 and 0.142 in the outlet, where the mass fractions of C2H6, C2H4, CO and CO2 were 0.035, 0.061, 0.032 and 0.106, respectively. Due to the existence of laminar boundary layer, the contours of each component bent upwards in the vicinity of the boundary layer. This OCM reaction was volume increase reaction and the total moles of products were greater than those of reactants. The flow field in the catalyst bed maintained constant temperature and pressure. The fluid density decreased gradually from 2.28 kg/m3 in the inlet of the catalyst bed to 2.22 kg/m3 in the outlet of the catalyst bed, while the velocity increased from 0.108 m/s to 0.115 m/s.展开更多
To perform an integral simulation of a pool-type reactor using CFD code,a multi-physics coupled code MPC-LBE for an LBE-cooled reactor was proposed by integrating a point kinetics model and a fuel pin heat transfer mo...To perform an integral simulation of a pool-type reactor using CFD code,a multi-physics coupled code MPC-LBE for an LBE-cooled reactor was proposed by integrating a point kinetics model and a fuel pin heat transfer model into self-developed CFD code.For code verification,a code-to-code comparison was employed to validate the CFD code.Furthermore,a typical BT transient benchmark on the LBE-cooled XADS reactor was selected for verification in terms of the integral or system performance.Based on the verification results,it was demonstrated that the MPC-LBE coupled code can perform thermal-hydraulics or safety analyses for analysis for processes involved in LBE-cooled pool-type reactors.展开更多
Flow characteristics, such as flow pattern, gas holdup, and bubble size distribution, in an internal loop reactor with external liquid circulation, are simulated to investigate the influence of reactor internals by us...Flow characteristics, such as flow pattern, gas holdup, and bubble size distribution, in an internal loop reactor with external liquid circulation, are simulated to investigate the influence of reactor internals by using the computational fluid dynamics （CFD）-population balance equations （PBE） coupled model. Numerical results reveal that introducing a downcomer tube and a draft tube can help to improve the mass and heat transfer of the reactor through enhanced liquid circulation, increased gas holdup and reduced bubble diameter. The hydrodynamic behavior in the internal loop reactor with external liquid circulation can be managed effectively by adjusting the diameter and axial position of the draft tube.展开更多
The fluid model,also called the macroscopic model,is commonly used to simulate low temperature and low pressure radiofrequency plasma discharges.By varying the parameters of the model,numerical simulation allows us to...The fluid model,also called the macroscopic model,is commonly used to simulate low temperature and low pressure radiofrequency plasma discharges.By varying the parameters of the model,numerical simulation allows us to study several cases,providing us the physico-chemical information that is often difficult to obtain experimentally.In this work,using the fluid model,we employ numerical simulation to show the effect of pressure and space between the reactor electrodes on the fundamental properties of silicon plasma diluted with ammonia and hydrogen.The results show the evolution of the fundamental characteristics of the plasma discharge as a function of the variation of the pressure and the distance between the electrodes.By examining the pressure-distance product in a range between 0.3 Torr 2.7 cm and 0.7 Torr 4 cm,we have determined the optimal pressure-distance product that allows better deposition of hydrogenated silicon nitride(SiN_(x)H_(y))films which is 0.7 Torr 2.7 cm.展开更多
The effect of temperature and hydrogen addition on undesired carbonaceous deposit formation during methane coupling was studied in DBD-plasma catalytic-wall reactors with Pd/Al2 O3, using electrical power to drive the...The effect of temperature and hydrogen addition on undesired carbonaceous deposit formation during methane coupling was studied in DBD-plasma catalytic-wall reactors with Pd/Al2 O3, using electrical power to drive the reaction.Experiments with thin catalyst layers allowed comparison of the performance of empty reactors and catalytic wall reactors without significantly influencing the plasma properties.The product distribution varies strongly in the temperature window between 25 and 200℃Minimal formation of deposits is found at an optimal temperature around 75℃ in the catalytic-wall reactors.The selectivity to deposits was c.a.10% with only 9 mg of catalyst loading instead of 45% in the blank reactor,while decreasing methane conversion only mildly.Co-feeding H2 to an empty reactor causes a similar decrease in selectivity to deposits,but in this case methane conversion also decreased significantly.Suppression of deposits formation in the catalytic-wall reactor at 75℃ is due to catalytic hydrogenation of mainly acetylene to ethylene.In the empty reactor,H2 co-feed decreases conversion but does not change the product distribution.The catalytic-wall reactors can be regenerated with H2-plasma at room temperature,which produces more added-value hydrocarbons.展开更多
This paper gives a numerical study on the flow and temperature fields in an induced plasma reactor, which worked in 0.5 ATM with air as a working gas. We employed a two-dimensional mode of an inductively coupled plas...This paper gives a numerical study on the flow and temperature fields in an induced plasma reactor, which worked in 0.5 ATM with air as a working gas. We employed a two-dimensional mode of an inductively coupled plasma to calculate the temperature and flow field of the reactor as well as the generator. The algorithm is based on the solutions of the two-dimensional continuity, momentum, and energy equations in term of vorticity, stream function and enthalpy. An upwind finite-difference scheme was adopted to solve those equations with appropriate boundary conditions. The computed results show that there is a flat region with little parameter change in the reactor, that the diameter of the region is not much larger than that of the generator and that a deep change of parameter exists in the outer side of the region.展开更多
A comprehensive kinetic model for oxidative coupling of methane（OCM）over Mn and/or W promoted Na2SO4/SiO2 catalysts was developed based on a micro-catalytic reactor data.The methane conversion and ethylene,ethane,ca...A comprehensive kinetic model for oxidative coupling of methane（OCM）over Mn and/or W promoted Na2SO4/SiO2 catalysts was developed based on a micro-catalytic reactor data.The methane conversion and ethylene,ethane,carbon monoxide and carbon dioxide selectivities were obtained in a wide operating condition range of 750 - 825-C,CH4/O2=2.5 - 10 and contact time=267 - 472 kg s m-3.Reaction networks of six models with different rate equation types were compared together.The kinetic rate parameters of each reaction network were estimated using linear regression or genetic algorithm optimization method（GA）.A reaction network suggested by Stansch et al.for OCM was found to be the best one and was further used in this work.The suggested model could predict the experimental results of OCM reaction within a deviation range of ± 20%.展开更多
The catalytic oxidative cou pling of methane(OCM)to C_(2) hydrocarbons(C_(2)H_(6) and C_(2)H_(4))represents one of the most effective ways to convert natural gas to more useful products,which can be performed effectiv...The catalytic oxidative cou pling of methane(OCM)to C_(2) hydrocarbons(C_(2)H_(6) and C_(2)H_(4))represents one of the most effective ways to convert natural gas to more useful products,which can be performed effectively using La_(0.6)Sr0.4Co_(0.2)Fe_(0.8)O_(3-δ)(LSCF)perovskite hollow fiber membrane microreactor.In this work,the effects of adding a thin BaCe_(0.8)Gd_(0.2)O_(3-δ)(BCG)catalyst film onto the inner LSCF fiber surface as the OCM catalyst and a porous Ba0.5Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)(BSCF)perovskite layer onto the outer LSCF surface to improve the oxygen permeation were evaluated.Between 700℃and 1000℃,methane conversion increased in the order of uncoated,BCG and BSCF-coated,and BCG-coated LSCF hollow fiber while Coselectivity and C_(2)-yield increased in the order of BCG and BSCF-coated,uncoated,and BCG-coated LSCF hollow fiber.Oxygen permeation flux at the same temperature range,on the other hand,was enhanced in the order of uncoated,BCG-coated,and BCG and BSCF-coated LSCF hollow fiber.This finding demonstrates the complex interplay between oxygen permeation and OCM performance.The BCG and BSCFcoated hollow fiber was also subjected to thermal cycles between 850℃and 900℃for up to 175 hours during which the fiber showed minor degradation in oxygen permeation fluxes and relatively stable OCM performance.展开更多
The group Ⅲ nitrides are an important class of materials with aplications in UV and visible optoelectronics,high temperature electronics,cold cathodes and solar blind detectors.In recent years,with the realisation of...The group Ⅲ nitrides are an important class of materials with aplications in UV and visible optoelectronics,high temperature electronics,cold cathodes and solar blind detectors.In recent years,with the realisation of nitride based LEDs,the use of GaN IED has the potential to compete with 1raditional filament and discharge lamps,for the provision of white lighting,and there has been an explosion of interest in the MOCVD growth of GaN based materials with an increasing focus on large area multiwafer reactors and wafer uniforrmity.This paper will review the design philosophy and characteristics of close-coupled showerhead reactors,relating these to the requirements of group Ⅲ-nitride growth,and will present a selection of data resulting from the operation of such equipment.These results suggest that the close coupled showerhead style of reactor is very suitable for the growth of GaN based structures in both research and production environments.展开更多
基金supported by the National Key R&D Program of China(2021YFF0500703)Natural Science Foundation of Shanghai(22JC1404200)+3 种基金Program of Shanghai Academic/Technology Research Leader(20XD1404000)Natural Science Foundation of China(U22B20136,22293023)Science and Technology Major Project of Inner Mongolia(2021ZD0042)the Youth Innovation Promotion Association of CAS。
文摘A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO_(2) photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the photon utilization efficiency for succinonitrile synthesis at room temperature.The space time yield of succinonitrile reached 55.59μmol/(g·h)over hydrophobic TiO_(2) catalyst,which was much higher than that of pristine TiO_(2)(4.23μmol/(g·h)).Mechanistic studies revealed that the hydrophobic modification of TiO_(2) promoted the separation and transfer of photogenerated carriers,as well as suppressed their recombination.Hydrophobic TiO_(2) also enhanced the adsorption of−CH3 of acetonitrile,thus facilitating the activation of C−H bond and the utilization efficiency of photocarriers.
文摘The oxidative coupling of methane （OCM） to ethylene over a perovskite titanate catalyst in a fixed bed reactor was studied experimentally and numerically. The two-dimensional steady state model accounted for separate energy equations for the gas and solid phases coupled with an experimental kinetic model. A lumped kinetic model containing four main species CH4, O2, COx （CO2, CO）, and C2 （C2H4 and C2H6） was used with a plug flow reactor model as well. The results from the model agreed with the experimental data. The model was used to analyze the influence of temperature and feed gas composition on the conversion and selectivity of the reactor performance. The analytical results indicate that the conversion decreases, whereas, C2 selectivity increases by increasing gas hourly space velocity （GHSV） and the methane conversion also decreases by increasing the methane to oxygen ratio.
文摘The study of scale up for the oxidative coupling of methane （OCM） has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 （W-Mn/SiO2） catalyst. The effects of reaction conditions were investigated in detail. The results showed that, with increasing reaction temperature, the gas-phase reaction was enhanced and a significant amount of methane was converted into COx; with the CH4/O2 molar ratio of 5, the highest C2 （ethylene and ethane） yield of 25% was achieved; the presence of steam （as diluent） had a positive effect on the C2 selectivity and yield. Under lower methane gaseous hourly space velocity （GHSV）, higher selectivity and yield of C2 were obtained as the result of the decrease of released heat energy. In 100 h reaction time, the C2 selectivity of 66%-61% and C2 yield of 24.2%-25.4% were achieved by a single pass without any significant loss in catalytic performance.
基金supported by Science and Technology on Reactor System Design Technology Laboratory,Chengdu,China(LRSDT2020106)
文摘In this study,a multi-physics and multi-scale coupling program,Fluent/KMC-sub/NDK,was developed based on the user-defined functions(UDF)of Fluent,in which the KMC-sub-code is a sub-channel thermal-hydraulic code and the NDK code is a neutron diffusion code.The coupling program framework adopts the"master-slave"mode,in which Fluent is the master program while NDK and KMC-sub are coupled internally and compiled into the dynamic link library(DLL)as slave codes.The domain decomposition method was adopted,in which the reactor core was simulated by NDK and KMC-sub,while the rest of the primary loop was simulated using Fluent.A simulation of the reactor shutdown process of M2LFR-1000 was carried out using the coupling program,and the code-to-code verification was performed with ATHLET,demonstrating a good agreement,with absolute deviation was smaller than 0.2%.The results show an obvious thermal stratification phenomenon during the shutdown process,which occurs 10 s after shutdown,and the change in thermal stratification phenomena is also captured by the coupling program.At the same time,the change in the neutron flux density distribution of the reactor was also obtained.
基金supported by the Chinese TMSR Strategic Pioneer Science and Technology Project(No.XDA02010000)the Frontier Science Key Program of the Chinese Academy of Sciences(No.QYZDY-SSW-JSC016)。
文摘In the core of a molten salt fast reactor(MSFR),heavy metal fuel and fission products can be dissolved in a molten fluoride salt to form a eutectic mixture that acts as both fuel and coolant.Fission energy is released from the fuel salt and transferred to the second loop by fuel salt circulation.Therefore,the MSFR is characterized by strong interaction between the neutronics and the thermal hydraulics.Moreover,recirculation flow occurs,and nuclear heat is accumulated near the fertile blanket,which significantly affects both the flow and the temperature fields in the core.In this work,to further optimize the conceptual geometric design of the MSFR,three geometries of the core and fertile blanket are proposed,and the thermal-hydraulic characteristics,including the three-dimensional flow and temperature fields of the fuel and fertile salts,are simulated and analyzed using a coupling scheme between the open source codes OpenMC and OpenFOAM.The numerical results indicate that a flatter core temperature distribution can be obtained and the hot spot and flow stagnation zones that appear in the upper and lower parts of the core center near the reflector can be eliminated by curving both the top and bottom walls of the core.Moreover,eight cooling loops with a total flow rate of0.0555 m3 s-1 ensur an acceptable temperature distribusure an acceptable temperature distribution in the fertile blanket.
基金supported by the National Basic Research Program of China(Project No. 2005CB221405)
文摘A dual-bed reactor was constructed comprising of a 5%Na2WO4-2%Mn/SiO2 particle catalyst and a 4%Ce-5%Na2WO4-2%Mn/SiO2 /cordierite monolithic catalyst.The reaction performance of the oxidative coupling of methane （OCM） over the dual-bed reactor system was evaluated.The effects of the bed height and operation mode,as well as the reaction parameters such as reaction temperature,CH4/O2 ratio and flowrate of feed gas,on the catalytic performance were investigated.The results indicated that the suggested dual-bed reactor exhibited a good performance for the OCM reaction when the feed gases firstly passed through the particle catalyst bed and then to the monolithic catalyst bed.A CH4 conversion of 38.2% and a C2H4 selectivity of 43.3% could be obtained using the dual-bed reactor with a particle catalyst bed height of 10 mm and a monolithic catalyst bed height of 50 mm.Both the CH4 conversion and C2H4 selectivity have increased by 2.5% and 12.8%,respectively,as compared with the 5%Na2WO4-2%Mn/SiO2 particle catalyst in a conventional single-bed reactor and by 12.9% and 23.0%,respectively,as compared with the 4%Ce-5%Na2WO4-2%Mn/SiO2 /cordierite monolithic catalyst in a single-bed reactor.The catalytic performance of the OCM in the dual-bed reactor system has been improved remarkably.
基金supported by the Deutsche Forschungsgemeinschaft (DFG)
文摘Performance of the oxidative coupling of methane in fluidized-bed reactor was experimentally investigated using Mn-Na2WO4/SiO2,La2O3/CaO and La2O3-SrO/CaO catalysts.These catalysts were found to be stable,especially Mn-Na2WO4/SiO2 catalyst.The effect of sodium content of this catalyst was analyzed and the challenge of catalyst agglomeration was addressed using proper catalyst composition of 2%Mn2.2%Na2WO4/SiO2.For other two catalysts,the effect of Lanthanum-Strontium content was analyzed and 10%La2O 3-20%SrO/CaO catalyst was found to provide higher ethylene yield than La2O3/CaO catalyst.Furthermore,the effect of operating parameters such as temperature and methane to oxygen ratio were also reviewed.The highest ethylene and ethane （C2） yield was achieved with the lowest methane to oxygen ratio around 2.40.5% selectivity to ethylene and ethane and 41% methane conversion were achieved over La2O3-SrO/CaO catalyst while over Mn-Na2WO4 /SiO2 catalyst,40% and 48% were recorded,respectively.Moreover,the consecutive effects of nitrogen dilution,ethylene to ethane production ratio and other performance indicators on the down-stream process units were qualitatively discussed and Mn-Na2WO4/SiO2 catalyst showed a better performance in the reactor and process scale analysis.
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The bifurcation behavior of the CO coupling reactor was examined based on the one-dimensional pseudo homogeneous axial dispersion dynamic model. The method of finite difference was used for solving the boundary value problem; the continuation technique and the direct method were applied to determine the bifurcation diagram. The effects of dimensionless adiabatic temperature rise, Damkohler number, activation energy, heat transfer coefficient and feed ratio on the bifurcation behavior were investigated. It was shown that there existed static bifurcation and the oscillations did not occur in the reactor. The result also revealed that the reactor exhibited at most 1-3-1 multiplicity patterns within the range of practical possible parameters and the measures, such as weakening the axial dispersion of reactor, enhancing heat transfer, decreasing the concentration of ethyl nitrite, were efficient for avoiding the possible risk of multiple steady states.
基金Supported by the National Basic Research Program of China(2005CB221405)
文摘A three-dimensional geometric model was set up for the oxidative coupling of methane(OCM) fixed bed reactor loaded with Na_3PO_4-Mn/SiO_2/cordierite monolithic catalyst,and an improved Stansch kinetic model was established to calculate the OCM reactions using the computational fluid dynamics method and Fluent software.The simulation conditions were completely the same with the experimental conditions that the volume velocity of the reactant is 80 ml·min^(-1) under standard state,the CH_4/O_2 ratio is 3 and the temperature and pressure is800 ℃ and 1 atm,respectively.The contour of the characteristic parameters in the catalyst bed was analyzed,such as the species mass fractions,temperature,the heat flux on side wall surface,pressure,fluid density and velocity.The results showed that the calculated values matched well with the experimental values on the conversion of CH4 and the selectivity of products(C_2H_6,C_2H_4,CO,CO_2 and H_2) in the reactor outlet with an error range of±4%.The mass fractions of CH_4 and O_2 decreased from 0.600 and 0.400 at the catalyst bed inlet to 0.445 and0.120 at the outlet,where the mass fractions of C_2H_6,C_2H_4,CO and CO_2 were 0.0245,0.0460,0.0537 and 0.116,respectively.Due to the existence of laminar boundary layer,the mass fraction contours of each species bent upwards in the vicinity of the boundary layer.The volume of OCM reaction was changing with the proceeding of reaction,and the total moles of products were greater than reactants.The flow field in the catalyst bed maintained constant temperature and pressure.The fluid density decreased gradually from 2.28 kg·m^(-3) at the inlet of the catalyst bed to 2.18 kg·m^(-3) at the outlet of the catalyst bed,while the average velocity magnitude increased from 0.108 m·s-1 to 0.120 m·s^(-1).
基金supported by Gansu Cuihua Technology Co.,Ltd.(H2020292)Science and Technology Planning of Baiyin City,Fundamental Research Funds for the Central Universities (buctrc202208)+2 种基金Engineering Research Center of Non-metallic Minerals of Zhejiang Province and the Beijing Engineering Center for Hierarchical Catalysts. Central Government Guiding Funds for Local Science and Technology Development (2022ZY015)Nanjiang Technology Project(2023AB028)Open Laboratory of State Key Laboratory of Organic and Inorganic Composites (oic-202301006)。
文摘Coupling adsorption and in-situ Fenton-like oxidation process was developed for Methylene blue(MB) using refined iron-containing lowgrade attapulgite(ATP) clay, and the removal mechanism was investigated. The MB was initially adsorbed on the porous ATPs, and then the enriched MB was removed by the H2O2-assisted Fenton-like oxidation with the iron-containing ATP catalyst. Under optimal conditions, the ATP powder exhibits the maximum removal efficiency of 100% with negligible iron leaching(1.5 mg L^(-1)) and no sludge formation. Furthermore,polysulfone/ATP(PSF/ATP) pellets were fabricated through a water-induced phase separation process to construct a fixed-bed reactor(FBR) for continuous contaminant removal. For the first cycle, the maximum adsorption capacity was 15.5 L with an outlet MB concentration of1.973 mg L-1(< 2 mg L^(-1), GB4287-2012) using the PSF/ATP pellets containing 50.0 g of ATP powders, and the maximum Fenton-like oxidation capacity was 35.5 L with the outlet concentration of 0.831 mg L^(-1). After five cycles, the total treated volume of the MB solution was ca. 255 L, and the efficiency remained above 99%. After 10 h of continuous treatment towards practical resin industrial wastewater, the chemical oxygen demand(COD) removal efficiency was still measured at 83.05%, costing 0.398 $ m^(-3). These results demonstrate the practical applicability of iron-containing low-grade ATP clay for textile water treatment.
文摘A three-dimensional geometric model of the oxidative coupling of methane （OCM） packed-bed reactor loaded with Na2WO4-Mn/SiO2 partic- ulate catalyst was set up, and an improved Stansch kinetic model was established to calculate the OCM reactions using the computational fluid dynamics method and Fluent software. The simulation conditions were completely the same with the experimental conditions that the volume velocity of the reactant was 80 mL/min under standard state, the ratio of CH4/O2 was 3, the temperature and pressure were 800 ℃ and 1 atm, respectively. The contour of the characteristics parameters in the catalyst bed was analyzed, such as the species mass fractions, temperature, the heat flux on side wall surface, pressure, fluid density and velocity. The results showed that the calculated values matched well with the experimental values on the conversion of CH4 and the selectivity to products （C2H6, C2H4, CO2, CO） in the reactor outlet with an error range of 4-2%. The mass fractions of CH4 and O2 decreased from 0.6 and 0.4 in the catalyst bed inlet to 0.436 and 0.142 in the outlet, where the mass fractions of C2H6, C2H4, CO and CO2 were 0.035, 0.061, 0.032 and 0.106, respectively. Due to the existence of laminar boundary layer, the contours of each component bent upwards in the vicinity of the boundary layer. This OCM reaction was volume increase reaction and the total moles of products were greater than those of reactants. The flow field in the catalyst bed maintained constant temperature and pressure. The fluid density decreased gradually from 2.28 kg/m3 in the inlet of the catalyst bed to 2.22 kg/m3 in the outlet of the catalyst bed, while the velocity increased from 0.108 m/s to 0.115 m/s.
基金supported by the National Natural Science Foundation of China(Nos.12005025,41774190).
文摘To perform an integral simulation of a pool-type reactor using CFD code,a multi-physics coupled code MPC-LBE for an LBE-cooled reactor was proposed by integrating a point kinetics model and a fuel pin heat transfer model into self-developed CFD code.For code verification,a code-to-code comparison was employed to validate the CFD code.Furthermore,a typical BT transient benchmark on the LBE-cooled XADS reactor was selected for verification in terms of the integral or system performance.Based on the verification results,it was demonstrated that the MPC-LBE coupled code can perform thermal-hydraulics or safety analyses for analysis for processes involved in LBE-cooled pool-type reactors.
基金Financial support from the Central Universities (12QN02)National Natural Science Foundation of China (51025624and 51076043)111 Project (B12034)
文摘Flow characteristics, such as flow pattern, gas holdup, and bubble size distribution, in an internal loop reactor with external liquid circulation, are simulated to investigate the influence of reactor internals by using the computational fluid dynamics （CFD）-population balance equations （PBE） coupled model. Numerical results reveal that introducing a downcomer tube and a draft tube can help to improve the mass and heat transfer of the reactor through enhanced liquid circulation, increased gas holdup and reduced bubble diameter. The hydrodynamic behavior in the internal loop reactor with external liquid circulation can be managed effectively by adjusting the diameter and axial position of the draft tube.
文摘The fluid model,also called the macroscopic model,is commonly used to simulate low temperature and low pressure radiofrequency plasma discharges.By varying the parameters of the model,numerical simulation allows us to study several cases,providing us the physico-chemical information that is often difficult to obtain experimentally.In this work,using the fluid model,we employ numerical simulation to show the effect of pressure and space between the reactor electrodes on the fundamental properties of silicon plasma diluted with ammonia and hydrogen.The results show the evolution of the fundamental characteristics of the plasma discharge as a function of the variation of the pressure and the distance between the electrodes.By examining the pressure-distance product in a range between 0.3 Torr 2.7 cm and 0.7 Torr 4 cm,we have determined the optimal pressure-distance product that allows better deposition of hydrogenated silicon nitride(SiN_(x)H_(y))films which is 0.7 Torr 2.7 cm.
基金supported by the Innovation Fund for Chemistry of NWO,grant number 731.014.303by SASOL。
文摘The effect of temperature and hydrogen addition on undesired carbonaceous deposit formation during methane coupling was studied in DBD-plasma catalytic-wall reactors with Pd/Al2 O3, using electrical power to drive the reaction.Experiments with thin catalyst layers allowed comparison of the performance of empty reactors and catalytic wall reactors without significantly influencing the plasma properties.The product distribution varies strongly in the temperature window between 25 and 200℃Minimal formation of deposits is found at an optimal temperature around 75℃ in the catalytic-wall reactors.The selectivity to deposits was c.a.10% with only 9 mg of catalyst loading instead of 45% in the blank reactor,while decreasing methane conversion only mildly.Co-feeding H2 to an empty reactor causes a similar decrease in selectivity to deposits,but in this case methane conversion also decreased significantly.Suppression of deposits formation in the catalytic-wall reactor at 75℃ is due to catalytic hydrogenation of mainly acetylene to ethylene.In the empty reactor,H2 co-feed decreases conversion but does not change the product distribution.The catalytic-wall reactors can be regenerated with H2-plasma at room temperature,which produces more added-value hydrocarbons.
文摘This paper gives a numerical study on the flow and temperature fields in an induced plasma reactor, which worked in 0.5 ATM with air as a working gas. We employed a two-dimensional mode of an inductively coupled plasma to calculate the temperature and flow field of the reactor as well as the generator. The algorithm is based on the solutions of the two-dimensional continuity, momentum, and energy equations in term of vorticity, stream function and enthalpy. An upwind finite-difference scheme was adopted to solve those equations with appropriate boundary conditions. The computed results show that there is a flat region with little parameter change in the reactor, that the diameter of the region is not much larger than that of the generator and that a deep change of parameter exists in the outer side of the region.
文摘A comprehensive kinetic model for oxidative coupling of methane（OCM）over Mn and/or W promoted Na2SO4/SiO2 catalysts was developed based on a micro-catalytic reactor data.The methane conversion and ethylene,ethane,carbon monoxide and carbon dioxide selectivities were obtained in a wide operating condition range of 750 - 825-C,CH4/O2=2.5 - 10 and contact time=267 - 472 kg s m-3.Reaction networks of six models with different rate equation types were compared together.The kinetic rate parameters of each reaction network were estimated using linear regression or genetic algorithm optimization method（GA）.A reaction network suggested by Stansch et al.for OCM was found to be the best one and was further used in this work.The suggested model could predict the experimental results of OCM reaction within a deviation range of ± 20%.
基金the research funding provided by the National Natural Science Foundation of China(21805206,22179073).
文摘The catalytic oxidative cou pling of methane(OCM)to C_(2) hydrocarbons(C_(2)H_(6) and C_(2)H_(4))represents one of the most effective ways to convert natural gas to more useful products,which can be performed effectively using La_(0.6)Sr0.4Co_(0.2)Fe_(0.8)O_(3-δ)(LSCF)perovskite hollow fiber membrane microreactor.In this work,the effects of adding a thin BaCe_(0.8)Gd_(0.2)O_(3-δ)(BCG)catalyst film onto the inner LSCF fiber surface as the OCM catalyst and a porous Ba0.5Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)(BSCF)perovskite layer onto the outer LSCF surface to improve the oxygen permeation were evaluated.Between 700℃and 1000℃,methane conversion increased in the order of uncoated,BCG and BSCF-coated,and BCG-coated LSCF hollow fiber while Coselectivity and C_(2)-yield increased in the order of BCG and BSCF-coated,uncoated,and BCG-coated LSCF hollow fiber.Oxygen permeation flux at the same temperature range,on the other hand,was enhanced in the order of uncoated,BCG-coated,and BCG and BSCF-coated LSCF hollow fiber.This finding demonstrates the complex interplay between oxygen permeation and OCM performance.The BCG and BSCFcoated hollow fiber was also subjected to thermal cycles between 850℃and 900℃for up to 175 hours during which the fiber showed minor degradation in oxygen permeation fluxes and relatively stable OCM performance.
文摘The group Ⅲ nitrides are an important class of materials with aplications in UV and visible optoelectronics,high temperature electronics,cold cathodes and solar blind detectors.In recent years,with the realisation of nitride based LEDs,the use of GaN IED has the potential to compete with 1raditional filament and discharge lamps,for the provision of white lighting,and there has been an explosion of interest in the MOCVD growth of GaN based materials with an increasing focus on large area multiwafer reactors and wafer uniforrmity.This paper will review the design philosophy and characteristics of close-coupled showerhead reactors,relating these to the requirements of group Ⅲ-nitride growth,and will present a selection of data resulting from the operation of such equipment.These results suggest that the close coupled showerhead style of reactor is very suitable for the growth of GaN based structures in both research and production environments.
