Cyanoethylation of phenylamine is one of the important steps for the production of dicyanoethyl-based disperse dyes.However,the exothermic nature of this reaction and the inherent instability of intermittent dynamic o...Cyanoethylation of phenylamine is one of the important steps for the production of dicyanoethyl-based disperse dyes.However,the exothermic nature of this reaction and the inherent instability of intermittent dynamic operation pose challenges in achieving both high safety and reaction efficiency.In this study,a continuous cyanoethylation of phenylamine for synthesizing N,N-dicyanoethylaniline in a microreactor system has been developed.By optimizing the reaction conditions,the reaction time was significantly reduced from over 2 h in batch operation to approximately 14 min in the microreactor,while high conversion and selectivity were maintained.Based on the reaction network constructed,the reaction kinetics was established,and the kinetic parameters were then determined.These findings provide valuable insights into a controllable cyanoethylation reaction,which would be helpful for the design of efficient processes and optimization of reactors.展开更多
Mixing behavior is critical for enhancing the selectivity of fast chemical reactions in microreactors.A high Reynolds number(Re)improves the mixing rate and selectivity of the reactions,but some exceptions of increasi...Mixing behavior is critical for enhancing the selectivity of fast chemical reactions in microreactors.A high Reynolds number(Re)improves the mixing rate and selectivity of the reactions,but some exceptions of increasing side product yield with the higher Re have been reported.This study investigated the mixing uniformity in microreactors with in-line UV-vis spectroscopy to clarify the relationship between reaction selectivity and chaotic mixing with the higher Re.A colorization experiment of thymolphthalein in an acidic solution was conducted with an excess acid amount to the base to indicate a non-uniformly mixed region.Non-uniformity significantly increased with Re.At the same time,the degree of mixing,which was measured by a usual decolorization experiment,showed that the mixing rate increased with Re.The in-line analysis of the Villermaux-Dushman reaction during the mixing clarified that side product yield significantly increased with Re at around 300 and then decreased at around 1100.These results suggest the compensation effect between the mixing uniformity and mixing rate on the selectivity of the mixing-sensitive reactions.Faster mixing,characterized by a larger Re,can disturb mixing uniformity and,in some cases,decrease reaction selectivity.展开更多
High-purity ethylene carbonate(EC)is widely used as battery electrolyte,polycarbonate monomer,organic intermediate,and so on.An economical and sustainable route to synthesize high-purity ethylene carbonate(EC)via the ...High-purity ethylene carbonate(EC)is widely used as battery electrolyte,polycarbonate monomer,organic intermediate,and so on.An economical and sustainable route to synthesize high-purity ethylene carbonate(EC)via the transesterification of dimethyl carbonate(DMC)with ethylene glycol(EG)is provided in this work.However,this reaction is so fast that the reaction kinetics,which is essential for the industrial design,is hard to get by the traditional measuring method.In this work,an easy-to-assemble microreactor was used to precisely determine the reaction kinetics for the fast transesterification of DMC with EG using sodium methoxide as catalyst.The effects of flow rate,microreactor diameter,catalyst concentration,reaction temperature,and reactant molar ratio were investigated.An activity-based pseudohomogeneous kinetic model,which considered the non-ideal properties of reaction system,was established to describe the transesterification of DMC with EG.Detailed kinetics data were collected in the first 5 min.Using these data,the parameters of the kinetic model were correlated with the maximum average error of 11.19%.Using this kinetic model,the kinetic data at different catalyst concentrations and reactant molar ratios were predicted with the maximum average error of 13.68%,suggesting its satisfactory prediction performance.展开更多
Gas-liquid-liquid three-phase slug flow was generated in both hydrophilic and hydrophobic microreactors with double T-junctions.The bubble-droplet relative movement and the local mass transfer within the continuous sl...Gas-liquid-liquid three-phase slug flow was generated in both hydrophilic and hydrophobic microreactors with double T-junctions.The bubble-droplet relative movement and the local mass transfer within the continuous slug and the dispersed droplet were investigated.It was found that bubbles moved faster than droplets under low capillary number(Ca),while droplets moved faster upon the increase of Ca due to the increased inertia.For the first time,we observed that the increased viscosity of droplets fastened the droplet movement.The mass transfer in the continuous slug was dominated by convection,leading to nearly constant global mass transfer coefficient(k_(L)a);while that in the dispersed droplet was dominated by diffusion,resulting in k_(L) decreasing along the channel.Such features are analogical to the corresponding gas-liquid or liquid-liquid two-phase slug flow,but the formation of bubble-droplet clusters caused by relative movement lowered the absolute mass transfer coefficient.These results provide insights for the precise manipulation of gas-liquid-liquid slug flow in microreactors towards process optimization.展开更多
Tonalid,an important fragrance ingredient with widespread applicatio n,was synthesized via two FriedelCrafts reactions,which were catalyzed by AlCl_(3).The traditional tonalid production was conducted in batch stirrin...Tonalid,an important fragrance ingredient with widespread applicatio n,was synthesized via two FriedelCrafts reactions,which were catalyzed by AlCl_(3).The traditional tonalid production was conducted in batch stirring tank reactors,suffering from low production capacity and the safety hazard of temperature runaway.To solve these problems,the continuous-flow technologies were developed for the highefficiency and intrinsically safe synthesis of tonalid in microreactors.Catalyst AlCl_(3)was neatly homogenized in proper solvents by forming complex with reactant,which was a necessary step for the continuous synthesis in microreactors.Several reaction conditions,including reactant molar ratio,catalyst concentration,temperature,and microchannel hydrodynamic diameter,were investigated for the two Friedel-Crafts reactions in micro reactors.At optimized conditions,the yields of the two Friedel-Crafts reactions were 44.15%and 97.55%,respectively.In comparison with the batch reactors,the reaction times of these two reactions could both be reduced by nearly two thirds in microreactors at the similar yield.展开更多
Microreactors are increasingly used for green and safe chemical processes owing to their benefits of superior mass and heat transfer,increased yield,safety,and simplicity of control.However,immobilizing catalysts in m...Microreactors are increasingly used for green and safe chemical processes owing to their benefits of superior mass and heat transfer,increased yield,safety,and simplicity of control.However,immobilizing catalysts in microreactors remains challenging.In this investigation,a technique for creating Cu_(2)O/montmorillonite catalyst coating,using electrostatic attraction for layer-by-layer self-assembly,was proposed.The montmorillonite film's morphology and thickness could be efficiently regulated by adjusting the degree of exfoliation and surface charge of montmorillonite,alongside layer-by-layer coating times.The Cu_(2)O nanoparticles were immobilized using the flow deposition approach.The resulting Cu_(2)O@montmorillonite-film-coated capillary microreactor successfully transformed glycerol into dihydroxyacetone.The conversion of glycerol and product selectivity could be controlled by adjusting the molar ratio of reactants,temperature,residence time,and Cu_(2)O loading.The maximum glycerol conversion observed was 47.6%,with a 27%selectivity toward dihydroxyacetone.The study presents a technique for immobilizing montmorillonite-based catalyst coatings in capillary tubing,which can serve as a foundation for the future application of microreactors in glycerol conversion.展开更多
Micromixing efficiency is an important parameter for evaluating the multiphase mass transfer performance and reaction efficiency of microreactors.In this work,the novel curved capillary reactor with different shapes w...Micromixing efficiency is an important parameter for evaluating the multiphase mass transfer performance and reaction efficiency of microreactors.In this work,the novel curved capillary reactor with different shapes was designed to generate Dean flow,which was used to enhance the liquid-liquid micromixing performance.The Villermaux-Dushman probe reaction was employed to characterize the micromixing performance in different curved capillary microreactors.The effects of experiment parameters such as liquid flow rate,inner diameter,tube length,and curve diameter on micromixing performance were systematically investigated.Under the optimal conditions,the minimum value of the segmentation factor XS was 0.008.It was worth noting that at the low Reynolds number(Re<30),the change of curved shape on the capillary microreactor can significantly improve the micromixing performance with XS reduced by 37.5%.Further,the correlations of segment index XS with dimensionless factor such as Reynolds number or Dean number were developed,which can be used to predict the liquid-liquid micromixing performance in capillary microreactors.展开更多
The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium prese...The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry.Here,we report the synthesis of FeOOH/Fe_(3)O_(4)/metal-organic framework(MOF)polygonal mesopores microflower templated from a MIL-88B(Fe)at room temperature,which exposes polygonal mesopores with atomistic edge steps and lattice defects.The obtained FeOOH/Fe_(3)O_(4)/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor.In the alkaline environment,oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA,showing impressive performance.This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture.The position and type of substituent critically affect the products.Additionally,this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities.Finally,the reactions can be conducted in a pressure reactor,which can conserve oxygen and prevent solvent loss.Moreover,compared with the traditional batch reactor,the self-built microchannel reactor can accelerate the reaction rate,shorten the reaction time,and enhance the selectivity of catalytic oxidation reactions.This approach contributes to environmental protection and holds potential for industrial applications.展开更多
The integration of microreactor and ultrasound represents an emerging area for process intensification and has attracted considerable attention in recent years.One of the most important meso-scientific issues in ultra...The integration of microreactor and ultrasound represents an emerging area for process intensification and has attracted considerable attention in recent years.One of the most important meso-scientific issues in ultrasound techniques is acoustic cavitation,which plays a vital role in the macroscopic performance of an ultrasonic microreactor.In this review,we first briefly summarize the latest research on acoustic cavitation phenomena in microreactors.The effects of channel configuration,solvent properties,and ultrasound parameters are systematically reviewed.In addition,the role of acoustic cavitation in various chemical processes(e.g.,mixing,absorption,emulsification,and particle synthesis)is presented from a mesoscale perspective,which in turn provides guidance for ultrasound applications.A thorough under-standing of the ultrasound intensification mechanism will contribute to the future development of this promising technology.展开更多
For the synthesis of AgInS_2 quantum dots(QDs), a suitable temperature is extremely important for control of the size, shape and fluorescence properties of QDs. Most of synthesis methods for AgInS_2 QDs are based on b...For the synthesis of AgInS_2 quantum dots(QDs), a suitable temperature is extremely important for control of the size, shape and fluorescence properties of QDs. Most of synthesis methods for AgInS_2 QDs are based on batch reactors, which bring uneven distribution of temperature, affecting their fluorescence properties and size uniformity. Here we designed a droplet microreactor with a temperature-controllable region, and successfully synthesized water-soluble AgInS_2 QDs. By accurately controlling temperature,we also studied how the reaction temperature affected the fluorescence properties of AgInS_2 QDs. The results showed that with the increasing of reaction temperature, the QDs size increased and the fluorescence peak constantly red-shifted along with enhanced fluorescence intensity. Based on the droplet microreactor, we could achieve more appropriate reaction condition to synthesize AgInS_2 QDs with higher fluorescence quantum yield(QY) and intensity.展开更多
An easy method is presented to fabricate monodisperse magnetic macroporous polymer beads(MMPBs). Waterin-oil high internal phase emulsion(HIPE) is prepared by emulsifying aqueous iron ions solution in an oil phase...An easy method is presented to fabricate monodisperse magnetic macroporous polymer beads(MMPBs). Waterin-oil high internal phase emulsion(HIPE) is prepared by emulsifying aqueous iron ions solution in an oil phase containing monomers. The HIPE is introduced into a simple microfluidic device to fabricate monodisperse(water-in-oil)-in-water double emulsion droplets. The droplets serve as microreactors to synthesize Fe3O4 nanoparticles and are on-line polymerized to form MMPBs. The prepared MMPBs display uniform size, interconnected porous structure, superparamagnetic behavior and uniform distribution of Fe3O4 in polymer matrix. The MMPBs are characterized by scanning electron microscopy(SEM), Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD), transmission electron microscopy(TEM), vibrating sample magnetometry(VSM). We believe that this method is a universal technique in preparing macroporous nanocomposite beads.展开更多
Aqueous phase synthesized ternary I-III-VI_(2) Quantum dots(QDs)are getting more and more attention in biology researches,for their good biocompatibility and easy-to-adjust fluorescence properties.However,the quantum ...Aqueous phase synthesized ternary I-III-VI_(2) Quantum dots(QDs)are getting more and more attention in biology researches,for their good biocompatibility and easy-to-adjust fluorescence properties.However,the quantum yield(QY)of these aqueous phase synthesized QDs are often pretty low,which seriously hindered their further applications in this field.In general,the ripening of the QDs helps to enhance their QY,closely related to the ripening temperature.But it is still hard to precisely control the fluorescence performance of the QDs products,due to the difficulties in precise temperature control and cumbersome temperature adjusting operations in batch reactors.Here we proposed an integrated droplet microfluidic chip for the automated and successive AgInS_(2)QDs synthesis and ripening,with both temperatures controlled independently,precisely but easily.Taking advantage of the space-time transformation of the droplet microfluidic chips,the suitable temperature combination for Ag In S_(2)QDs synthesis and ripening was studied,and the high-performance AgInS_(2)QDs were obtained.In addition,the reason for the decrease of QY of AgInS_(2)QDs at higher ripening temperature was also explored.展开更多
Based on microreactors, the representative Baylis-Hillman reaction of cyclopent-2-enone coupled with 4-nitrobenzaldehyde in the presence of imidazole could be accelerated by manipulating the temperature and electric f...Based on microreactors, the representative Baylis-Hillman reaction of cyclopent-2-enone coupled with 4-nitrobenzaldehyde in the presence of imidazole could be accelerated by manipulating the temperature and electric field. Furthermore, the electric field was used in promoting Baylis-Hillman reaction for the first time with the rate acceleration approximately 5.2-fold higher than that carried out in conventional vessels as well as 4.0-fold under control of temperature. Meanwhile, the products of Baylis-Hillman reaction at every time point could be collected and then determined by capillary micellar electrokinetic chromatography.展开更多
To address the energy challenges,scientists have designed various artificial light-harvesting systems inspired by photosynthesis.Notably,for light-harvesting systems,an energytransfer efficiency close to 100%with an a...To address the energy challenges,scientists have designed various artificial light-harvesting systems inspired by photosynthesis.Notably,for light-harvesting systems,an energytransfer efficiency close to 100%with an antenna effect greater than 10 is generally considered a good application criterion.[1]Today,building an efficient light-harvesting system at a low cost is still demanding.展开更多
A new microreactor with continuous serially connected micromixers(CSCM)was tailored for the coprecipitation process to synthesize Fe_(3)O_(4) nanoparticles.Numerical simulation reveals that the two types of CSCM micro...A new microreactor with continuous serially connected micromixers(CSCM)was tailored for the coprecipitation process to synthesize Fe_(3)O_(4) nanoparticles.Numerical simulation reveals that the two types of CSCM microchannels(V-typed and U-typed)proposed in this work exhibited markedly better mixing performances than the Zigzag and capillary microchannels due to the promotion of Dean vortices.Complete mixing was achieved in the V-typed microchannel in 2.7 s at an inlet Reynolds number of 27.Fe_(3)O_(4) nanoparticles synthesized in a planar glass microreactor with the V-typed microchannel,possessing an average size of 9.3 nm and exhibiting superparamagnetism,had obviously better dispersity and uniformity and higher crystallinity than those obtained in the capillary microreactor.The new CSCM microreactor developed in this work can act as a potent device to intensify the synthesis of similar inorganic nanoparticles via multistep chemical precipitation processes.展开更多
Ligand assisted reprecipitation(LARP)is a widely used method for cesium lead halide perovskite nanocrystals(NCs)synthesis.Nevertheless,the ultrafast kinetics of LARP,as well as the inefficient transport properties and...Ligand assisted reprecipitation(LARP)is a widely used method for cesium lead halide perovskite nanocrystals(NCs)synthesis.Nevertheless,the ultrafast kinetics of LARP,as well as the inefficient transport properties and discontinuity of batch reactors,challenge the particle size control and experimental repeatability.To address these issues,an ultrasonic cavitation-enabled microfluidic approach was developed to achieve the continuous synthesis of cesium lead halide perovskite via LARP.It was found that the mixing between the good solvent and antisolvent in the microchannel was greatly enhanced by intensive ultrasonic cavitation.The mixing time could be reduced to below 10 ms under the irradiation of 35 W ultrasound.By modulating the mixing degree,LARP was proved to be a mixing-sensitive process.The effects of ultrasonic power,ultrasonic treatment time,total flow rate,water additive,and reprecipitation temperature on the synthesis of CsPbBr_(3) NCs were systematically investigated.As compared to CsPbBr_(3) NCs synthesized in the batch reactor,the sample synthesized via the ultrasonic cavitation-enabled microfluidic approach possessed stronger photoluminescence intensity and better repeatability.Moreover,the ultrasonic cavitation-enabled microfluidic approach could also realize the continuous synthesis of cesium lead halide perovskite NCs with different halide compositions to cover a wide visible spectrum(426-661 nm).The ultrasonic cavitation-enabled microfluidic approach paved the way for the large-scale of high-quality cesium lead halide perovskite NCs.展开更多
The wall wettability of microchannels plays an important role in the gas-liquid mass transfer dynamics under Taylor flow.In this study,we regulated the contact angle of the wall surface through surface chemical grafti...The wall wettability of microchannels plays an important role in the gas-liquid mass transfer dynamics under Taylor flow.In this study,we regulated the contact angle of the wall surface through surface chemical grafting polymerization under controlled experimental conditions.The dynamic changes of CO_(2)bubbles flowing along the microchannel were captured by a high-speed video camera mounted on a stereo microscope,whilst a unit cell model was employed to theoretically investigate the gas-liquid mass transfer dynamics.We quantitatively characterized the effects of wall wettability,specifically the contact angle,on the formation mechanism of gas bubbles and mass transfer process experimentally.The results revealed that the gas bubble velocity,the overall volumetric liquid phase mass transfer coefficients(kLa),and the specific interfacial area(a)all increased with the increase of the contact angle.Conversely,gas bubble length and leakage flow decreased.Furthermore,we proposed a new modified model to predict the gas-liquid two-phase mass transfer performance,based on van Baten’s and Yao’s models.Our proposed model was observed to agree reasonably well with experimental observations.展开更多
Mass transfer performance of gas–liquid two-phase flow at microscale is the basis of application of microreactor in gas–liquid reaction systems.At present,few researches on the mass transfer property of annular flow...Mass transfer performance of gas–liquid two-phase flow at microscale is the basis of application of microreactor in gas–liquid reaction systems.At present,few researches on the mass transfer property of annular flow have been reported.Therefore,the mass transfer mechanism and relationship of gas–liquid annular flow in a microfluidic cross-junction device are studied in the present study.We find that the main factors,i.e.,flow pattern,liquid film thickness,liquid hydraulic retention time,phase interface fluctuation,and gas flow vorticity,which influence the flow mass transfer property,are directly affected both by gas and liquid flow velocities.But the influences of gas and liquid velocities on different mass transfer influencing factors are different.Thereout,the fitting relationships between gas and liquid flow velocities and mass transfer influencing factors are established.By comparing the results from calculations using fitting equations and simulations,it shows that the fitting equations have relatively high degrees of accuracy.Finally,the Pareto front,namely the Pareto optimal solution set,of gas and liquid velocity conditions for the best flow mass transfer property is obtained using the method of multi-objective particle swarm optimization.It is proved that the mass transfer property of the gas–liquid two-phase flow can be obviously enhanced under the guidance of the obtained Pareto optimal solution set through experimental verification.展开更多
1-Oxa-2-azaspiro[2.5]octane,as one of N-H oxaziridines,is a selective electrophilic aminating agent for N-,S-,C-,and O-nucleophiles.It has the features of stereoselectivity and the absence of formation of strongly aci...1-Oxa-2-azaspiro[2.5]octane,as one of N-H oxaziridines,is a selective electrophilic aminating agent for N-,S-,C-,and O-nucleophiles.It has the features of stereoselectivity and the absence of formation of strongly acidic or basic byproducts,leading to considerable interest in the development of organic synthetic methods.Currently,the economically feasible route of production of 1-oxa-2-azaspiro[2.5]octane is the reaction of cyclohexanone with ammonia and sodium hypochlorite.However,due to strong exothermic reactions,massive gas release and heterogeneous reaction,the controllability,efficiency and safety of the reaction are in great difficulty using batch technology.In this paper,a microreaction system containing predispersion,reaction and phase separation was introduced into the preparation of 1-oxa-2-azaspiro[2.5]octane.The research results showed that precise control of the process including droplet dispersion,temperature control,reaction time control and fast continuous phase separation,was the key to process intensification.Under optimal conditions,the concentration of 1-oxa-2-azaspiro[2.5]octane in product obtained by microreaciton system(~2.0 mol·L^(-1))was much higher than that obtained by batch technology(0.2-0.4 mol·L^(-1)),which demonstrated that the continuous-flow synthesis would be a more efficient substitute for batch synthesis.Meanwhile,the results of the derivation experiments also showed that the aminating agent solution with higher concentration was more advantageous in the applications.展开更多
The transfer rate between fluids in a microreactor is directly influenced by the mixing within the reactor, which subsequently impacts the reaction rate. This paper investigates the flow behavior and macro-mixing perf...The transfer rate between fluids in a microreactor is directly influenced by the mixing within the reactor, which subsequently impacts the reaction rate. This paper investigates the flow behavior and macro-mixing performance in a microreactor. First, the flow performance of the Ehrfeld Miprowa microreactor is studied. Cold experiments are conducted to examine fundamental flow laws and verify the accuracy of the chosen computational fluid dynamics simulation model.Subsequently, macro-mixing performance in the microreactor, both with and without internal components, is investigated through both experiment and simulation. A bromocresol violet–NaOH–H2SO4 system is utilized in the macro-mixing experiments, which explore the effects of flow rate and internal components on macro-mixing. The Navier–Stokes equation is adopted as the computational model for macro-mixing simulations, which also consider the mass transfer and diffusion of tracer. The simulation results are in good agreement with the experimental results. Both experimental and simulation results demonstrate that the presence of internal components in the microreactor enhance its macro-mixing performance.展开更多
基金the financial supports from National Natural Science Foundation of China(22378344,22208278)Natural Science Foundation of Shandong Province(ZR2023MB120,ZR2023QB152)Youth Innovation Team Plan of Shandong Province(2022KJ270)。
文摘Cyanoethylation of phenylamine is one of the important steps for the production of dicyanoethyl-based disperse dyes.However,the exothermic nature of this reaction and the inherent instability of intermittent dynamic operation pose challenges in achieving both high safety and reaction efficiency.In this study,a continuous cyanoethylation of phenylamine for synthesizing N,N-dicyanoethylaniline in a microreactor system has been developed.By optimizing the reaction conditions,the reaction time was significantly reduced from over 2 h in batch operation to approximately 14 min in the microreactor,while high conversion and selectivity were maintained.Based on the reaction network constructed,the reaction kinetics was established,and the kinetic parameters were then determined.These findings provide valuable insights into a controllable cyanoethylation reaction,which would be helpful for the design of efficient processes and optimization of reactors.
基金the support of JSPS KAKENHI(21H05083)the Cooperative Research Program of the Network Joint Research Center for Materials and Devices,which was supported by the Ministry of Education,Culture,Sports,Science,and Technology(MEXT),JapanAUN/SEED-Net(BUU REd-UC 2301)for Research and Education Grant for the University Consortium(consortium name:CES-CHEM)。
文摘Mixing behavior is critical for enhancing the selectivity of fast chemical reactions in microreactors.A high Reynolds number(Re)improves the mixing rate and selectivity of the reactions,but some exceptions of increasing side product yield with the higher Re have been reported.This study investigated the mixing uniformity in microreactors with in-line UV-vis spectroscopy to clarify the relationship between reaction selectivity and chaotic mixing with the higher Re.A colorization experiment of thymolphthalein in an acidic solution was conducted with an excess acid amount to the base to indicate a non-uniformly mixed region.Non-uniformity significantly increased with Re.At the same time,the degree of mixing,which was measured by a usual decolorization experiment,showed that the mixing rate increased with Re.The in-line analysis of the Villermaux-Dushman reaction during the mixing clarified that side product yield significantly increased with Re at around 300 and then decreased at around 1100.These results suggest the compensation effect between the mixing uniformity and mixing rate on the selectivity of the mixing-sensitive reactions.Faster mixing,characterized by a larger Re,can disturb mixing uniformity and,in some cases,decrease reaction selectivity.
基金support for this work from the National Natural Science Foundation of China(21706034)the Natural Science Foundation of Fujian Province(2021J01645)the Key Program of Qingyuan Innovation Laboratory(00221004).
文摘High-purity ethylene carbonate(EC)is widely used as battery electrolyte,polycarbonate monomer,organic intermediate,and so on.An economical and sustainable route to synthesize high-purity ethylene carbonate(EC)via the transesterification of dimethyl carbonate(DMC)with ethylene glycol(EG)is provided in this work.However,this reaction is so fast that the reaction kinetics,which is essential for the industrial design,is hard to get by the traditional measuring method.In this work,an easy-to-assemble microreactor was used to precisely determine the reaction kinetics for the fast transesterification of DMC with EG using sodium methoxide as catalyst.The effects of flow rate,microreactor diameter,catalyst concentration,reaction temperature,and reactant molar ratio were investigated.An activity-based pseudohomogeneous kinetic model,which considered the non-ideal properties of reaction system,was established to describe the transesterification of DMC with EG.Detailed kinetics data were collected in the first 5 min.Using these data,the parameters of the kinetic model were correlated with the maximum average error of 11.19%.Using this kinetic model,the kinetic data at different catalyst concentrations and reactant molar ratios were predicted with the maximum average error of 13.68%,suggesting its satisfactory prediction performance.
基金the financial support for this work from National Natural Science Foundation of China(21991103,92034303,91634204)。
文摘Gas-liquid-liquid three-phase slug flow was generated in both hydrophilic and hydrophobic microreactors with double T-junctions.The bubble-droplet relative movement and the local mass transfer within the continuous slug and the dispersed droplet were investigated.It was found that bubbles moved faster than droplets under low capillary number(Ca),while droplets moved faster upon the increase of Ca due to the increased inertia.For the first time,we observed that the increased viscosity of droplets fastened the droplet movement.The mass transfer in the continuous slug was dominated by convection,leading to nearly constant global mass transfer coefficient(k_(L)a);while that in the dispersed droplet was dominated by diffusion,resulting in k_(L) decreasing along the channel.Such features are analogical to the corresponding gas-liquid or liquid-liquid two-phase slug flow,but the formation of bubble-droplet clusters caused by relative movement lowered the absolute mass transfer coefficient.These results provide insights for the precise manipulation of gas-liquid-liquid slug flow in microreactors towards process optimization.
基金financial support for this work from the National Natural Science Foundation of China(No.21706034)the Natural Science Foundation of Fujian Province(No.2021J01645)the Key Program of Qingyuan Innovation Laboratory(No.00221004)。
文摘Tonalid,an important fragrance ingredient with widespread applicatio n,was synthesized via two FriedelCrafts reactions,which were catalyzed by AlCl_(3).The traditional tonalid production was conducted in batch stirring tank reactors,suffering from low production capacity and the safety hazard of temperature runaway.To solve these problems,the continuous-flow technologies were developed for the highefficiency and intrinsically safe synthesis of tonalid in microreactors.Catalyst AlCl_(3)was neatly homogenized in proper solvents by forming complex with reactant,which was a necessary step for the continuous synthesis in microreactors.Several reaction conditions,including reactant molar ratio,catalyst concentration,temperature,and microchannel hydrodynamic diameter,were investigated for the two Friedel-Crafts reactions in micro reactors.At optimized conditions,the yields of the two Friedel-Crafts reactions were 44.15%and 97.55%,respectively.In comparison with the batch reactors,the reaction times of these two reactions could both be reduced by nearly two thirds in microreactors at the similar yield.
基金support from the National Natural Science Foundation of China(2207213641672033)+2 种基金the research grants from Engineering Research Center of Non-metallic Minerals of Zhejiang Province(ZD2023K01)the projects from Qing Yang Institute for Industrial Minerals(KYYHX-20220336KYY-HX-20170557).
文摘Microreactors are increasingly used for green and safe chemical processes owing to their benefits of superior mass and heat transfer,increased yield,safety,and simplicity of control.However,immobilizing catalysts in microreactors remains challenging.In this investigation,a technique for creating Cu_(2)O/montmorillonite catalyst coating,using electrostatic attraction for layer-by-layer self-assembly,was proposed.The montmorillonite film's morphology and thickness could be efficiently regulated by adjusting the degree of exfoliation and surface charge of montmorillonite,alongside layer-by-layer coating times.The Cu_(2)O nanoparticles were immobilized using the flow deposition approach.The resulting Cu_(2)O@montmorillonite-film-coated capillary microreactor successfully transformed glycerol into dihydroxyacetone.The conversion of glycerol and product selectivity could be controlled by adjusting the molar ratio of reactants,temperature,residence time,and Cu_(2)O loading.The maximum glycerol conversion observed was 47.6%,with a 27%selectivity toward dihydroxyacetone.The study presents a technique for immobilizing montmorillonite-based catalyst coatings in capillary tubing,which can serve as a foundation for the future application of microreactors in glycerol conversion.
基金supports of National Natural Science Foundation of China(22308057)Outstanding Talent Introduction Funds from Fuzhou University(0040-511175)Fuzhou University Testing Fund of precious apparatus(2023T003).
文摘Micromixing efficiency is an important parameter for evaluating the multiphase mass transfer performance and reaction efficiency of microreactors.In this work,the novel curved capillary reactor with different shapes was designed to generate Dean flow,which was used to enhance the liquid-liquid micromixing performance.The Villermaux-Dushman probe reaction was employed to characterize the micromixing performance in different curved capillary microreactors.The effects of experiment parameters such as liquid flow rate,inner diameter,tube length,and curve diameter on micromixing performance were systematically investigated.Under the optimal conditions,the minimum value of the segmentation factor XS was 0.008.It was worth noting that at the low Reynolds number(Re<30),the change of curved shape on the capillary microreactor can significantly improve the micromixing performance with XS reduced by 37.5%.Further,the correlations of segment index XS with dimensionless factor such as Reynolds number or Dean number were developed,which can be used to predict the liquid-liquid micromixing performance in capillary microreactors.
基金supported by the National Natural Science Foundation of China(22078251)Hubei Province Key Research and Development Program(2023DJC167)the research project of Hubei Provincial Department of Education(D20191504).
文摘The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry.Here,we report the synthesis of FeOOH/Fe_(3)O_(4)/metal-organic framework(MOF)polygonal mesopores microflower templated from a MIL-88B(Fe)at room temperature,which exposes polygonal mesopores with atomistic edge steps and lattice defects.The obtained FeOOH/Fe_(3)O_(4)/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor.In the alkaline environment,oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA,showing impressive performance.This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture.The position and type of substituent critically affect the products.Additionally,this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities.Finally,the reactions can be conducted in a pressure reactor,which can conserve oxygen and prevent solvent loss.Moreover,compared with the traditional batch reactor,the self-built microchannel reactor can accelerate the reaction rate,shorten the reaction time,and enhance the selectivity of catalytic oxidation reactions.This approach contributes to environmental protection and holds potential for industrial applications.
基金This work was supported by the National Natural Science Foun-dation of China(No.91634204)the Youth Innovation Promotion Association CAS(No.2017229)Dalian Science&Technology Innovation Fund(No.2018J11CY019).
文摘The integration of microreactor and ultrasound represents an emerging area for process intensification and has attracted considerable attention in recent years.One of the most important meso-scientific issues in ultrasound techniques is acoustic cavitation,which plays a vital role in the macroscopic performance of an ultrasonic microreactor.In this review,we first briefly summarize the latest research on acoustic cavitation phenomena in microreactors.The effects of channel configuration,solvent properties,and ultrasound parameters are systematically reviewed.In addition,the role of acoustic cavitation in various chemical processes(e.g.,mixing,absorption,emulsification,and particle synthesis)is presented from a mesoscale perspective,which in turn provides guidance for ultrasound applications.A thorough under-standing of the ultrasound intensification mechanism will contribute to the future development of this promising technology.
基金supported by the National Natural Science Foundation of China (Nos. 21375100, 21775111)the National Science and Technology Major Project of China (No. 2018ZX10301405)
文摘For the synthesis of AgInS_2 quantum dots(QDs), a suitable temperature is extremely important for control of the size, shape and fluorescence properties of QDs. Most of synthesis methods for AgInS_2 QDs are based on batch reactors, which bring uneven distribution of temperature, affecting their fluorescence properties and size uniformity. Here we designed a droplet microreactor with a temperature-controllable region, and successfully synthesized water-soluble AgInS_2 QDs. By accurately controlling temperature,we also studied how the reaction temperature affected the fluorescence properties of AgInS_2 QDs. The results showed that with the increasing of reaction temperature, the QDs size increased and the fluorescence peak constantly red-shifted along with enhanced fluorescence intensity. Based on the droplet microreactor, we could achieve more appropriate reaction condition to synthesize AgInS_2 QDs with higher fluorescence quantum yield(QY) and intensity.
文摘An easy method is presented to fabricate monodisperse magnetic macroporous polymer beads(MMPBs). Waterin-oil high internal phase emulsion(HIPE) is prepared by emulsifying aqueous iron ions solution in an oil phase containing monomers. The HIPE is introduced into a simple microfluidic device to fabricate monodisperse(water-in-oil)-in-water double emulsion droplets. The droplets serve as microreactors to synthesize Fe3O4 nanoparticles and are on-line polymerized to form MMPBs. The prepared MMPBs display uniform size, interconnected porous structure, superparamagnetic behavior and uniform distribution of Fe3O4 in polymer matrix. The MMPBs are characterized by scanning electron microscopy(SEM), Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD), transmission electron microscopy(TEM), vibrating sample magnetometry(VSM). We believe that this method is a universal technique in preparing macroporous nanocomposite beads.
基金supported by the National Natural Science Foundation of China(Nos.22074107,21775111)。
文摘Aqueous phase synthesized ternary I-III-VI_(2) Quantum dots(QDs)are getting more and more attention in biology researches,for their good biocompatibility and easy-to-adjust fluorescence properties.However,the quantum yield(QY)of these aqueous phase synthesized QDs are often pretty low,which seriously hindered their further applications in this field.In general,the ripening of the QDs helps to enhance their QY,closely related to the ripening temperature.But it is still hard to precisely control the fluorescence performance of the QDs products,due to the difficulties in precise temperature control and cumbersome temperature adjusting operations in batch reactors.Here we proposed an integrated droplet microfluidic chip for the automated and successive AgInS_(2)QDs synthesis and ripening,with both temperatures controlled independently,precisely but easily.Taking advantage of the space-time transformation of the droplet microfluidic chips,the suitable temperature combination for Ag In S_(2)QDs synthesis and ripening was studied,and the high-performance AgInS_(2)QDs were obtained.In addition,the reason for the decrease of QY of AgInS_(2)QDs at higher ripening temperature was also explored.
基金Project supported by Ministry of Science and Technology of China (No. 2007CB714504), the National Natural Science Foundation of China (Nos. 20875091, 20935005) and Chinese Academy of Sciences.
文摘Based on microreactors, the representative Baylis-Hillman reaction of cyclopent-2-enone coupled with 4-nitrobenzaldehyde in the presence of imidazole could be accelerated by manipulating the temperature and electric field. Furthermore, the electric field was used in promoting Baylis-Hillman reaction for the first time with the rate acceleration approximately 5.2-fold higher than that carried out in conventional vessels as well as 4.0-fold under control of temperature. Meanwhile, the products of Baylis-Hillman reaction at every time point could be collected and then determined by capillary micellar electrokinetic chromatography.
文摘To address the energy challenges,scientists have designed various artificial light-harvesting systems inspired by photosynthesis.Notably,for light-harvesting systems,an energytransfer efficiency close to 100%with an antenna effect greater than 10 is generally considered a good application criterion.[1]Today,building an efficient light-harvesting system at a low cost is still demanding.
基金the financial support from the National Natural Science Foundation of China(21808059)the Fundamental Research Funds for the Central Universities(JKA01221712).
文摘A new microreactor with continuous serially connected micromixers(CSCM)was tailored for the coprecipitation process to synthesize Fe_(3)O_(4) nanoparticles.Numerical simulation reveals that the two types of CSCM microchannels(V-typed and U-typed)proposed in this work exhibited markedly better mixing performances than the Zigzag and capillary microchannels due to the promotion of Dean vortices.Complete mixing was achieved in the V-typed microchannel in 2.7 s at an inlet Reynolds number of 27.Fe_(3)O_(4) nanoparticles synthesized in a planar glass microreactor with the V-typed microchannel,possessing an average size of 9.3 nm and exhibiting superparamagnetism,had obviously better dispersity and uniformity and higher crystallinity than those obtained in the capillary microreactor.The new CSCM microreactor developed in this work can act as a potent device to intensify the synthesis of similar inorganic nanoparticles via multistep chemical precipitation processes.
基金the financial supports from National Natural Science Foundation of China(22178336 and 21991103).
文摘Ligand assisted reprecipitation(LARP)is a widely used method for cesium lead halide perovskite nanocrystals(NCs)synthesis.Nevertheless,the ultrafast kinetics of LARP,as well as the inefficient transport properties and discontinuity of batch reactors,challenge the particle size control and experimental repeatability.To address these issues,an ultrasonic cavitation-enabled microfluidic approach was developed to achieve the continuous synthesis of cesium lead halide perovskite via LARP.It was found that the mixing between the good solvent and antisolvent in the microchannel was greatly enhanced by intensive ultrasonic cavitation.The mixing time could be reduced to below 10 ms under the irradiation of 35 W ultrasound.By modulating the mixing degree,LARP was proved to be a mixing-sensitive process.The effects of ultrasonic power,ultrasonic treatment time,total flow rate,water additive,and reprecipitation temperature on the synthesis of CsPbBr_(3) NCs were systematically investigated.As compared to CsPbBr_(3) NCs synthesized in the batch reactor,the sample synthesized via the ultrasonic cavitation-enabled microfluidic approach possessed stronger photoluminescence intensity and better repeatability.Moreover,the ultrasonic cavitation-enabled microfluidic approach could also realize the continuous synthesis of cesium lead halide perovskite NCs with different halide compositions to cover a wide visible spectrum(426-661 nm).The ultrasonic cavitation-enabled microfluidic approach paved the way for the large-scale of high-quality cesium lead halide perovskite NCs.
基金the financial supports from National Natural Science Foundation of China(21978250,22208278)Natural Science Foundation of Shandong Province(ZR2020KB013,ZR2020QE211,2019KJC012).
文摘The wall wettability of microchannels plays an important role in the gas-liquid mass transfer dynamics under Taylor flow.In this study,we regulated the contact angle of the wall surface through surface chemical grafting polymerization under controlled experimental conditions.The dynamic changes of CO_(2)bubbles flowing along the microchannel were captured by a high-speed video camera mounted on a stereo microscope,whilst a unit cell model was employed to theoretically investigate the gas-liquid mass transfer dynamics.We quantitatively characterized the effects of wall wettability,specifically the contact angle,on the formation mechanism of gas bubbles and mass transfer process experimentally.The results revealed that the gas bubble velocity,the overall volumetric liquid phase mass transfer coefficients(kLa),and the specific interfacial area(a)all increased with the increase of the contact angle.Conversely,gas bubble length and leakage flow decreased.Furthermore,we proposed a new modified model to predict the gas-liquid two-phase mass transfer performance,based on van Baten’s and Yao’s models.Our proposed model was observed to agree reasonably well with experimental observations.
基金the National Natural Science Foundation of China(22178241,21908152 and 21978189)State Key Laboratory of Chemical Engineering,China(SKL-ChE-21A01).
文摘Mass transfer performance of gas–liquid two-phase flow at microscale is the basis of application of microreactor in gas–liquid reaction systems.At present,few researches on the mass transfer property of annular flow have been reported.Therefore,the mass transfer mechanism and relationship of gas–liquid annular flow in a microfluidic cross-junction device are studied in the present study.We find that the main factors,i.e.,flow pattern,liquid film thickness,liquid hydraulic retention time,phase interface fluctuation,and gas flow vorticity,which influence the flow mass transfer property,are directly affected both by gas and liquid flow velocities.But the influences of gas and liquid velocities on different mass transfer influencing factors are different.Thereout,the fitting relationships between gas and liquid flow velocities and mass transfer influencing factors are established.By comparing the results from calculations using fitting equations and simulations,it shows that the fitting equations have relatively high degrees of accuracy.Finally,the Pareto front,namely the Pareto optimal solution set,of gas and liquid velocity conditions for the best flow mass transfer property is obtained using the method of multi-objective particle swarm optimization.It is proved that the mass transfer property of the gas–liquid two-phase flow can be obviously enhanced under the guidance of the obtained Pareto optimal solution set through experimental verification.
基金the support of the National Natural Science Foundation of China(22108264)for this work。
文摘1-Oxa-2-azaspiro[2.5]octane,as one of N-H oxaziridines,is a selective electrophilic aminating agent for N-,S-,C-,and O-nucleophiles.It has the features of stereoselectivity and the absence of formation of strongly acidic or basic byproducts,leading to considerable interest in the development of organic synthetic methods.Currently,the economically feasible route of production of 1-oxa-2-azaspiro[2.5]octane is the reaction of cyclohexanone with ammonia and sodium hypochlorite.However,due to strong exothermic reactions,massive gas release and heterogeneous reaction,the controllability,efficiency and safety of the reaction are in great difficulty using batch technology.In this paper,a microreaction system containing predispersion,reaction and phase separation was introduced into the preparation of 1-oxa-2-azaspiro[2.5]octane.The research results showed that precise control of the process including droplet dispersion,temperature control,reaction time control and fast continuous phase separation,was the key to process intensification.Under optimal conditions,the concentration of 1-oxa-2-azaspiro[2.5]octane in product obtained by microreaciton system(~2.0 mol·L^(-1))was much higher than that obtained by batch technology(0.2-0.4 mol·L^(-1)),which demonstrated that the continuous-flow synthesis would be a more efficient substitute for batch synthesis.Meanwhile,the results of the derivation experiments also showed that the aminating agent solution with higher concentration was more advantageous in the applications.
基金supported by the National Natural Science Foundation of China (No. 5197050207)。
文摘The transfer rate between fluids in a microreactor is directly influenced by the mixing within the reactor, which subsequently impacts the reaction rate. This paper investigates the flow behavior and macro-mixing performance in a microreactor. First, the flow performance of the Ehrfeld Miprowa microreactor is studied. Cold experiments are conducted to examine fundamental flow laws and verify the accuracy of the chosen computational fluid dynamics simulation model.Subsequently, macro-mixing performance in the microreactor, both with and without internal components, is investigated through both experiment and simulation. A bromocresol violet–NaOH–H2SO4 system is utilized in the macro-mixing experiments, which explore the effects of flow rate and internal components on macro-mixing. The Navier–Stokes equation is adopted as the computational model for macro-mixing simulations, which also consider the mass transfer and diffusion of tracer. The simulation results are in good agreement with the experimental results. Both experimental and simulation results demonstrate that the presence of internal components in the microreactor enhance its macro-mixing performance.