Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded...Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded organic frameworks(HOFs)have promising application potential for embedding enzymes.In fact,no metal involvement is required,and HOFs exhibit superior biocompatibility,and free access to substrates in mesoporous channels.Herein,a facile in situ growth approach was proposed for the self-assembly of alcohol dehydrogenase encapsulated in HOF.The micron-scale bio-catalytic composite was rapidly synthesized under mild conditions(aqueous phase and ambient temperature)with a controllable embedding rate.The high crystallinity and periodic arrangement channels of HOF were preserved at a high enzyme encapsulation efficiency of 59%.This bio-composite improved the tolerance of the enzyme to the acid-base environment and retained 81%of its initial activity after five cycles of batch hydrogenation involving NADH coenzyme.Based on this controllably synthesized bio-catalytic material and a common lipase,we further developed a two-stage cascade microchemical system and achieved the continuous production of chiral hydroxybutyric acid(R-3-HBA).展开更多
To get high purity caprolactam is a challenging task in the chemical fiber industry. To date, reports on the prediction of the distribution of caprolactam and its derivative chemicals have been few. In this study, the...To get high purity caprolactam is a challenging task in the chemical fiber industry. To date, reports on the prediction of the distribution of caprolactam and its derivative chemicals have been few. In this study, the extraction of caprolactam with toluene as the extractant and N-methyl caprolactam with benzene and toluene as theextractants has been camed out. By defining new UNIFAC groups and calibrating related interaction parameters, aUNIFAC method was introduced to predict the equilibrium concentration of caprolactam and methyl caprolactam intoluene or benzene extraction processes. The calculated results fit very well With the experimental data. Using theUNIFAC model, the selectivity of extractants can be predicted.展开更多
Microfluidic technology has been successfully applied to determine the reaction kinetics relying on its great characteristics including narrow residence time distribution,fast mixing,high mass and heat transfer rates ...Microfluidic technology has been successfully applied to determine the reaction kinetics relying on its great characteristics including narrow residence time distribution,fast mixing,high mass and heat transfer rates and very low consumption of materials.In this review,the recent progresses about the reaction kinetics measured in microreactors are comprehensively organized,and the kinetic modeling thoughts,determination methods and essential kinetic regularities contained in these studies are summarized according to the reaction types involving nitration,oxidation,hydrogenation,photochemical reaction,polymerization and other reactions.Besides,the significant advances in the innovation of microplatform are also covered.The novel reactor configuration methods were established mainly to achieve rapid and efficient data collection and analysis.Finally,the advantages of microfluidic technology for the kinetic measurement are summarized,and a perspective for the future development is provided.展开更多
Hydrotreating of vacuum residue by ebullated-bed shows tremendous significance due to more stringent environmental regulations and growing demand for lighter fuels. However, enhancing the catalyst stability still rema...Hydrotreating of vacuum residue by ebullated-bed shows tremendous significance due to more stringent environmental regulations and growing demand for lighter fuels. However, enhancing the catalyst stability still remains as a challenging task. Herein, two Ni–Mo/Al_(2)O_(3) catalysts with distinct morphologies(i.e., spherical and cylindrical) were first designed, and the morphology effect on deactivation was systematically elucidated employing multi-characterizations, such as HRTEM with EDX mapping, electron microprobe analysis, FT-IR, TGA and Raman. It is found that spherical catalyst exhibits superior hydrotreating stability over 1600 h. The carbonaceous deposits on spherical catalyst with less graphite structure are lighter, and the coke weight is also smaller. In addition, the metal deposits uniformly distribute in the spherical catalyst, which is better than the concentrated distribution near the pore mouth for the cylindrical catalyst. Furthermore, the intrinsic reason for the differences was analyzed by the bed expansion experiment. Higher bed expansion rate together with the better mass transfer ability leads to the enhanced performance. This work sheds new light on the design of more efficient industrial hydrotreating catalyst based on morphology effect.展开更多
In the extraction method for preparing KH2PO4, one of the key processes is the selective extraction of HCI over H3PO4. In our work, extraction kinetic studies have been carried out in a microfluidic device with a coax...In the extraction method for preparing KH2PO4, one of the key processes is the selective extraction of HCI over H3PO4. In our work, extraction kinetic studies have been carried out in a microfluidic device with a coaxial microchannel, using the extractant of 33.3% （by volume） trioctylamine （TOA） dissolved in n-octanol, with differ- ent aqueous phases： the HCI solution, the H3P04 solution, and H3PO4 and KCI solutions of different concentra- tions. The changes of the extraction efficiency of HC1 and H3P04 and the selectivity for HC1 along with the residence time were investigated. We found that fast extraction kinetics could be realized in microfluidic devices, and that HC1 could be extracted faster than H3P04 due to smaller mass transfer resistance and much stronger re- action between HCI and TOA. For the extraction of H3PO4 and KC1 solutions, the selectivity for HC1 first increased and then decreased when TOA was in excess of H3PO4 in the initial feeds, and in contrast, always increased when H3PO4 was in excess of TOA in the initial feeds. The diverse changes of selectivity for HCI along with the residence time indicate that a dynamic control of selectivity in microfluidic devices may be important and accessible for im- proving the KH2P04 conversion efficiency in extraction method.展开更多
A numerical investigation of the unsteady motion of a deformed drop released freely in another quiescent liquid contaminated by surfactant is presented in this paper. The finite difference method was used to solve num...A numerical investigation of the unsteady motion of a deformed drop released freely in another quiescent liquid contaminated by surfactant is presented in this paper. The finite difference method was used to solve numerically the coupled time-dependent Navier-Stokes and convective-diffusion equations in a body-fitted orthogonal coordinate system. Numerical simulation was conducted on the experimental cases, in which MIBK drops with the size ranging from 1.24 mm to 1.97 mm rose and accelerated freely in pure water and in dilute sodium dodecyl sulphate (SDS) aqueous solution. The applicability of the numerical scheme was validated by the agreement between the simulation results and the experimental data. Both the numerical and experimental results showed that the velocitytime profile exhibited a maximum rising velocity for drops in SDS solutions, which was close to the terminal velocity in pure water, before it dropped down to a steady-state value. The effect of the sorption kinetics of surfactant on the accelerating motion was also evaluated. It is also suggested that introduction of virtual mass force into the formulation improved obviously the precision of numerical simulation of transient drop motion.展开更多
Multiphase emulsions could be used as templates in considerable fields such as coating, optical materials, stan- dard particles and biomedicine. Among various emulsion forming methods, microfluidic technology, with go...Multiphase emulsions could be used as templates in considerable fields such as coating, optical materials, stan- dard particles and biomedicine. Among various emulsion forming methods, microfluidic technology, with good monodispersity, high controllability and operation simplicity, has been widely used in the preparation of multi- phase emulsions with different systems. This review would focus on the basic principles of forming multiphase emulsions, the recent progress in controlling multiphase flow in microfluidics, and preparation of functional ma- terials with microfluidics mainly by the authors＇ research group. We believe that the review will contribute to the readers in this prospective area very well. ~ 2016 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.展开更多
3-Methylpyridine-N-oxide is an essential intermediate in the preparation of 2-chloro-5-methylpyridine,which can be used to synthesize nicotine insecticides such as imidacloprid and acetamiprid.The traditional method o...3-Methylpyridine-N-oxide is an essential intermediate in the preparation of 2-chloro-5-methylpyridine,which can be used to synthesize nicotine insecticides such as imidacloprid and acetamiprid.The traditional method of production of 3-methylpyridine-N-oxide is catalytic oxidation of 3-methylpyridine in semi-batch reactors.Due to strong exothermic reaction and explosive property of 3-methylpyridine,the reaction efficiency and safety is low using batch technology.Therefore,the development of a safer and efficient 3-methylpyridine-N-oxide production process is very necessary in industrial production.In this paper,microreaction systems were introduced into the preparation of 3-methylpyridine-N-oxide.The comparison of three different methods(traditional semibatch method,co-current microreaction method,and circular microreaction method)showed that the circular microreaction method was the most applicable,with relative higher product yield(~90%),less side reaction and better reaction control.展开更多
Two pH-responsive amphiphilic diblock copolymers, namely polyisobutylene-block-poly[2-（N,N- dimethylamino）ethyl methaerylate] （PIB-b-PDMAEMA） and polyisobutylene-block-poly（metharylic acid） （PIB-b-PMAA）, were ...Two pH-responsive amphiphilic diblock copolymers, namely polyisobutylene-block-poly[2-（N,N- dimethylamino）ethyl methaerylate] （PIB-b-PDMAEMA） and polyisobutylene-block-poly（metharylic acid） （PIB-b-PMAA）, were synthesized via oxyanion-initiated polymerization, and their multiple self-assembly behaviors have been studied. An exo-01efin-terminated highly reactive polyisobutylene （HRPIB） was first changed to hydroxyl-terminated PIB （PIB-OH） via hydroboration-oxidation of C =C double bond in the chain end, and then reacted with KH to yield a potassium alcoholate of PIB （PIB-O-K＋）. PIB-O-K＋ was immediately used as a macroinitiator to polymerize DMAEMA monomer, resulting in a cationic diblock copolymer PIB-b-PDMAEMA. With the similar synthesis procedure, the anionic diblock copolymer PIB-b- PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate （tBMA） and subsequent hydrolysis of tert-butyl ester groups in PtBMA block. The functional PIB and block copolymers have been fully characterized by 1H-NMR, FT-IR spectroscopy, and gel permeation chromatography （GPC）. These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent. Transmission electron microscopy （TEM） images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles, vesicles with different particle sizes and cylindrical aggregates, depending on various factors including block copolymer composition, solvent polarity and pH value.展开更多
Eliminating topological defects to achieve monodomain liquid crystals is highly significant for the fundamental studies of soft matter and building long-range ordered materials.However,liquid crystals are metastable a...Eliminating topological defects to achieve monodomain liquid crystals is highly significant for the fundamental studies of soft matter and building long-range ordered materials.However,liquid crystals are metastable and sensitive to external stimuli,such as flow,confinement,and electromagnetic fields,which cause their intrinsic polycrystallinity and topological defects.Here,we achieve the monodomain liquid crystals of graphene oxide over 30 cm through boundary-free sheargraphy.The obtained monodomain liquid crystals exhibit large-area uniform alignment of sheets,which has the same optical polarized angle and intensity.The monodomain liquid crystals provide bidirectionally ordered skeletons,which can be applied as lightweight thermal management materials with bidirectionally high thermal and electrical conductivity.Furthermore,we extend the controllable topology of two-dimensional colloids by introducing singularities and disclinations in monodomain liquid crystals.Topological structures with defect strength from−2 to+2 were realized.This work provides a facile methodology to study the structural order of soft matter at a macroscopic level,facilitating the fabrication of metamaterials with tunable and highly anisotropic architectures.展开更多
The bimetallic nanoparticles compositing of Ni-rich core and Cu-rich shell(Ni/Cu NPs)were successfully synthesized by a liquid-phase thermal decomposition method.The content of copper and nickel in Ni/Cu NPs was contr...The bimetallic nanoparticles compositing of Ni-rich core and Cu-rich shell(Ni/Cu NPs)were successfully synthesized by a liquid-phase thermal decomposition method.The content of copper and nickel in Ni/Cu NPs was controllable by adjusting the ratio of two metal precursors,copper formate(Cuf)and nickel acetate tetrahydrate(Ni(OAc)_(2)·4H_(2)O).Ni/Cu NPs were further anchored on graphene oxide(GO)to prepare a magnetic composite catalyst,called Ni/Cu-GO.The dispersibility of Ni/Cu NPs in solution was enhanced by GO anchoring to prevent the sintering and aggregation during the reaction process,thereby ensuring the catalytic and cycling performance of the catalyst.The catalytic transfer hydrogenation(CTH)reaction of nitroaromatics was investigated when ammonia borane was used as the hydrogen source.Cu dominated the main catalytic role in the reaction,while Ni played a synergistic role of catalysis and providing magnetic properties for separation.The Ni_(7)/Cu_(3)-GO catalyst exhibited the best catalytic performance with the conversion and yield of 99%and 96%,respectively,when 2-methyl-5-nitrophenol was used as the substrate.The Ni_(7)/Cu_(3)-GO catalyst also exhibited excellent cyclic catalytic performance with the 5-amino-2-methylphenol yield of above 90%after six cycles.In addition,the Ni_(7)/Cu_(3)-GO catalyst could be quickly recycled by magnetic separation.Moreover,the Ni_(7)/Cu_(3)-GO catalyst showed good catalytic performance for halogen-containing nitroaromatics without dehalogenation.展开更多
It has long been found that the flow pattern of the liquid phase on distillation tray is of great importance on distillation process performance. But until now, there was very few published work on quantitative invest...It has long been found that the flow pattern of the liquid phase on distillation tray is of great importance on distillation process performance. But until now, there was very few published work on quantitative investigation of this subject. By combining the computational fluid dynamics (CFD) with the mass transfer equation, a theoretical model is proposed for predicting the details of velocity and concentration distributions as well as the tray efficiency of distillation tray column. Using the proposed model, four different cases corresponding to different assumptions of liquid and vapor flowing condition for a distillation tray column were investigated. In Case I, the distributions of velocity and concentration of the incoming liquid from the downcomer and the uprising vapor from the underneath tray spacing are uniform. In Case n, the distribution of the incoming liquid is non-uniform but the uprising vapor is uniform. In Case HI, the distribution of the incoming liquid is uniform but the uprising vapor is non-uniform. In Case IV, the distributions of both the incoming liquid and the uprising vapor are non-uniform. The details of velocity and concentration distributions on a multiple sieve tray distillation column in four different cases were simulated using the proposed model. It is found that the shape of the simulated concentration profiles of vapor and the liquid is quite different from case to case. The computed results also show that the tray efficiency is highly reduced by the maldistribution of velocity and concentration of the incoming liquid and uprising vapor. The tray efficiency for Case I is higher than Case Ⅱ or Case Ⅲ, and that for Case Ⅳ is the lowest. It also reveals that the accumulated effect of maldistribution becomes more pronounced when the number of column trays increased. The present study demonstrates that the use of computational method to predict the mass transfer efficiency for the tray column, especially for the large one, is feasible.展开更多
Two different solvents had been used to separate benzene from 1-hexene under atmosphere pressure by employing one of the following two solvents, viz.: dimethyl sulfoxide (DMSO) at 298.15 K and 318.15 K, and furfural a...Two different solvents had been used to separate benzene from 1-hexene under atmosphere pressure by employing one of the following two solvents, viz.: dimethyl sulfoxide (DMSO) at 298.15 K and 318.15 K, and furfural at 298.15 K. A series of liquid-liquid equilibrium (LLE) data had been obtained and the distribution coefficient together with the separation factor were calculated from them. Both the NRTL and the UNIQUAC models could fit in with the experimental data quite well.展开更多
Experimental investigation of the microfiltration （MF） using a revolving cross-flow membrane filter was performed under the condition of constant pressure difference, and different flat membranes made of polyvinylid...Experimental investigation of the microfiltration （MF） using a revolving cross-flow membrane filter was performed under the condition of constant pressure difference, and different flat membranes made of polyvinylidene fluoride （PVDF, 0.1 μm）, cellulose acetate （CA, 0.22 μm）, sulfonated polyethersulfone （SPES, 0.22 μm） and polyamide （PA, 0.45 μm）, respectively, were used in filtration experiments. The dependence of the filtrate mass of the cross-flow MF on time was measured on-line. The experimental results showed that the effect of the cross-flow on high viscosity medium was more significant than that on the low viscosity one.展开更多
In this article, a theoretical model for predicting the equilibrium morphology of gas–liquid Janus droplets was built. Based on this model, the effects of bubble radius and volume ratio on morphology change was syste...In this article, a theoretical model for predicting the equilibrium morphology of gas–liquid Janus droplets was built. Based on this model, the effects of bubble radius and volume ratio on morphology change was systematically studied. The increase of bubble radius causes the two parts(bubble and oil drop) in Janus droplets tend to merge while the impact of volume ratio is complicated. When volume ratio increases, these two parts firstly tend to merge, then gradually separate. The accuracy of this model was verified by experimental results.展开更多
The effects of potassium ferricyanide,sodium n-dodecyl sulfate,sodium hydroxide and temperature on the molecular weight and the yield of poly(2,6-dimethyl-1,4-phenylene oxide)(PPO) synthesized in an aqueous medium wer...The effects of potassium ferricyanide,sodium n-dodecyl sulfate,sodium hydroxide and temperature on the molecular weight and the yield of poly(2,6-dimethyl-1,4-phenylene oxide)(PPO) synthesized in an aqueous medium were studied.It was found that oxygen in air had little influence on the oxidative polymerization of 2,6-dimethylphenol(DMP) in the aqueous medium,and potassium ferricyanide was only an oxidant during the oxidative polymerization of DMP.Sodium n-dodecyl sulfate could stabilize polymer particles an...展开更多
As one of the most important catalysts in polyethylene industry,Phillips catalyst(CrO_x/SiO_2)was quite unique for its activation by ethylene monomer without using any activator like alkyl-aluminium or MAO.In this wor...As one of the most important catalysts in polyethylene industry,Phillips catalyst(CrO_x/SiO_2)was quite unique for its activation by ethylene monomer without using any activator like alkyl-aluminium or MAO.In this work,the density functional theory(DFT)calculation combined with paired interacting orbitals(PIO)method was applied for the theoretical studies on coordination reaction mechanism between ethylene monomer and two model catalysts namely Cr(Ⅱ)(OH)_2(M1) and silsesquioxane-supported Cr(Ⅱ)(M2)as surfac...展开更多
A mathematical model is developed for the calculation of the nucleation and growth process of silica nanostructured particles prepared by using the drop-by-drop method,and the calculation results of the proposed model...A mathematical model is developed for the calculation of the nucleation and growth process of silica nanostructured particles prepared by using the drop-by-drop method,and the calculation results of the proposed model is compared with the experimental value obtained from SAXS data.The model provides a non-ideal improvement in the supersaturation calculation and considers the impact of both mass transfer and surface reaction on the particle growth rate.The nucleation and growth rates are coupled depending on the change in monomer concentration over time,based on which the particle size and distribution are calculated.The growth curve of the silica particles from 3 nm to 20 nm and the change in particle number from 0 to over 10^(20) are calculated,which are consistent with the experimental values,establishing the reliability of the model.The calculations of the growth rate reveal that mass transfer controls the growth of silica particles before 10 min and the surface reaction is the rate-determining step after 10 min.The changes in the model parameters obtained by fitting with the SAXS data under different reaction conditions indicate the sensitivity of the corresponding process to different conditions.Moreover,the relationship between the particle growth rate and monomer concentration change is analyzed using the proposed model.展开更多
The methanolysis of amides,which is widely employed in the synthetic organic chemistry,hardly occurs under mild conditions.To safely and controllably intensify the methanolysis reaction with hightemperature and high-p...The methanolysis of amides,which is widely employed in the synthetic organic chemistry,hardly occurs under mild conditions.To safely and controllably intensify the methanolysis reaction with hightemperature and high-pressure environment,a continuous tubular reaction technology is developed,whose space-time yield is over twice of that of the conventional batch reaction.The methanolysis of acetanilide is selected as the representative reaction,and the influences of temperature,pressure,reactant and catalyst concentration,and residence time on the reaction performances are systematically investigated.Taking the advantages of precise temperature and reaction time control by the tubular reactor,the kinetics of acetanilide methanolysis are determined and compared to the kinetics of acetanilide hydrolysis reaction.The tubular reaction method is also employed to test a variety of other amides to show the effects of substituents,steric hindrance,and alkalinity on the reaction rate of methanolysis.展开更多
In this article Florian Puchtler at affiliation‘University of Bayreuth’,Josef Breu at affiliation‘University of Bayreuth’,and Ziliang Wu at affiliation‘Zhejiang University’was missing from the author Min Cao,Sen...In this article Florian Puchtler at affiliation‘University of Bayreuth’,Josef Breu at affiliation‘University of Bayreuth’,and Ziliang Wu at affiliation‘Zhejiang University’was missing from the author Min Cao,Senping Liu,Qingli Zhu,Ya Wang,Jingyu Ma,Zeshen Li,Dan Chang,Enhui Zhu,Xin Ming,Florian Puchtler,Josef Breu,Ziliang Wu,Yingjun Liu,Yanqiu Jiang,Zhen Xu,Chao Gao list.展开更多
基金supported by the National Key Research and Development Program of China(2019YFA0905100)the National Natural Science Foundation of China(21991102,22378227).
文摘Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded organic frameworks(HOFs)have promising application potential for embedding enzymes.In fact,no metal involvement is required,and HOFs exhibit superior biocompatibility,and free access to substrates in mesoporous channels.Herein,a facile in situ growth approach was proposed for the self-assembly of alcohol dehydrogenase encapsulated in HOF.The micron-scale bio-catalytic composite was rapidly synthesized under mild conditions(aqueous phase and ambient temperature)with a controllable embedding rate.The high crystallinity and periodic arrangement channels of HOF were preserved at a high enzyme encapsulation efficiency of 59%.This bio-composite improved the tolerance of the enzyme to the acid-base environment and retained 81%of its initial activity after five cycles of batch hydrogenation involving NADH coenzyme.Based on this controllably synthesized bio-catalytic material and a common lipase,we further developed a two-stage cascade microchemical system and achieved the continuous production of chiral hydroxybutyric acid(R-3-HBA).
基金Supported by the National Natural Science Foundation of China （No.20490200, No.20525622）.
文摘To get high purity caprolactam is a challenging task in the chemical fiber industry. To date, reports on the prediction of the distribution of caprolactam and its derivative chemicals have been few. In this study, the extraction of caprolactam with toluene as the extractant and N-methyl caprolactam with benzene and toluene as theextractants has been camed out. By defining new UNIFAC groups and calibrating related interaction parameters, aUNIFAC method was introduced to predict the equilibrium concentration of caprolactam and methyl caprolactam intoluene or benzene extraction processes. The calculated results fit very well With the experimental data. Using theUNIFAC model, the selectivity of extractants can be predicted.
基金support from National Natural Science Foundation of China(21991104).
文摘Microfluidic technology has been successfully applied to determine the reaction kinetics relying on its great characteristics including narrow residence time distribution,fast mixing,high mass and heat transfer rates and very low consumption of materials.In this review,the recent progresses about the reaction kinetics measured in microreactors are comprehensively organized,and the kinetic modeling thoughts,determination methods and essential kinetic regularities contained in these studies are summarized according to the reaction types involving nitration,oxidation,hydrogenation,photochemical reaction,polymerization and other reactions.Besides,the significant advances in the innovation of microplatform are also covered.The novel reactor configuration methods were established mainly to achieve rapid and efficient data collection and analysis.Finally,the advantages of microfluidic technology for the kinetic measurement are summarized,and a perspective for the future development is provided.
基金supported by Natural Science Foundation of China(21978325)the National Key Technologies Research and Development Program of China(2017YFB0306503)+5 种基金Fundamental Research Funds for the Central Universities(18CX02130A,18CX02014A)Open Project of State Key Laboratory of Chemical Engineering(SKL-Ch E-18C04)Doctoral Start-up Foundation of Liaoning Province(2019-BS054)Program for Liaoning Innovative Talents in University(XLYC1807245)China Postdoctoral Science Foundation(2019M661409)High-level Talent Innovation and Business Project of Dalian(2017RQ085)。
文摘Hydrotreating of vacuum residue by ebullated-bed shows tremendous significance due to more stringent environmental regulations and growing demand for lighter fuels. However, enhancing the catalyst stability still remains as a challenging task. Herein, two Ni–Mo/Al_(2)O_(3) catalysts with distinct morphologies(i.e., spherical and cylindrical) were first designed, and the morphology effect on deactivation was systematically elucidated employing multi-characterizations, such as HRTEM with EDX mapping, electron microprobe analysis, FT-IR, TGA and Raman. It is found that spherical catalyst exhibits superior hydrotreating stability over 1600 h. The carbonaceous deposits on spherical catalyst with less graphite structure are lighter, and the coke weight is also smaller. In addition, the metal deposits uniformly distribute in the spherical catalyst, which is better than the concentrated distribution near the pore mouth for the cylindrical catalyst. Furthermore, the intrinsic reason for the differences was analyzed by the bed expansion experiment. Higher bed expansion rate together with the better mass transfer ability leads to the enhanced performance. This work sheds new light on the design of more efficient industrial hydrotreating catalyst based on morphology effect.
基金Supported by the National Natural Science Foundation of China(91334201)
文摘In the extraction method for preparing KH2PO4, one of the key processes is the selective extraction of HCI over H3PO4. In our work, extraction kinetic studies have been carried out in a microfluidic device with a coaxial microchannel, using the extractant of 33.3% （by volume） trioctylamine （TOA） dissolved in n-octanol, with differ- ent aqueous phases： the HCI solution, the H3P04 solution, and H3PO4 and KCI solutions of different concentra- tions. The changes of the extraction efficiency of HC1 and H3P04 and the selectivity for HC1 along with the residence time were investigated. We found that fast extraction kinetics could be realized in microfluidic devices, and that HC1 could be extracted faster than H3P04 due to smaller mass transfer resistance and much stronger re- action between HCI and TOA. For the extraction of H3PO4 and KC1 solutions, the selectivity for HC1 first increased and then decreased when TOA was in excess of H3PO4 in the initial feeds, and in contrast, always increased when H3PO4 was in excess of TOA in the initial feeds. The diverse changes of selectivity for HCI along with the residence time indicate that a dynamic control of selectivity in microfluidic devices may be important and accessible for im- proving the KH2P04 conversion efficiency in extraction method.
基金Supported by the National Natural Science Foundation of China(No.20236050)
文摘A numerical investigation of the unsteady motion of a deformed drop released freely in another quiescent liquid contaminated by surfactant is presented in this paper. The finite difference method was used to solve numerically the coupled time-dependent Navier-Stokes and convective-diffusion equations in a body-fitted orthogonal coordinate system. Numerical simulation was conducted on the experimental cases, in which MIBK drops with the size ranging from 1.24 mm to 1.97 mm rose and accelerated freely in pure water and in dilute sodium dodecyl sulphate (SDS) aqueous solution. The applicability of the numerical scheme was validated by the agreement between the simulation results and the experimental data. Both the numerical and experimental results showed that the velocitytime profile exhibited a maximum rising velocity for drops in SDS solutions, which was close to the terminal velocity in pure water, before it dropped down to a steady-state value. The effect of the sorption kinetics of surfactant on the accelerating motion was also evaluated. It is also suggested that introduction of virtual mass force into the formulation improved obviously the precision of numerical simulation of transient drop motion.
基金Supported by the National Natural Science Foundation of China(21322604,21476121,21136006)NSAF(U1530107)+1 种基金the National Basic Research Programof China(2012CBA01203)and Tsinghua University Initiative Scientific Research Program(2014z21026)
文摘Multiphase emulsions could be used as templates in considerable fields such as coating, optical materials, stan- dard particles and biomedicine. Among various emulsion forming methods, microfluidic technology, with good monodispersity, high controllability and operation simplicity, has been widely used in the preparation of multi- phase emulsions with different systems. This review would focus on the basic principles of forming multiphase emulsions, the recent progress in controlling multiphase flow in microfluidics, and preparation of functional ma- terials with microfluidics mainly by the authors＇ research group. We believe that the review will contribute to the readers in this prospective area very well. ~ 2016 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.
基金the supports of the National Natural Science Foundation of China(21991101,2191100)the Key Project of Science&Technology Department of Sichuan Province(2017JZ0011)for this work。
文摘3-Methylpyridine-N-oxide is an essential intermediate in the preparation of 2-chloro-5-methylpyridine,which can be used to synthesize nicotine insecticides such as imidacloprid and acetamiprid.The traditional method of production of 3-methylpyridine-N-oxide is catalytic oxidation of 3-methylpyridine in semi-batch reactors.Due to strong exothermic reaction and explosive property of 3-methylpyridine,the reaction efficiency and safety is low using batch technology.Therefore,the development of a safer and efficient 3-methylpyridine-N-oxide production process is very necessary in industrial production.In this paper,microreaction systems were introduced into the preparation of 3-methylpyridine-N-oxide.The comparison of three different methods(traditional semibatch method,co-current microreaction method,and circular microreaction method)showed that the circular microreaction method was the most applicable,with relative higher product yield(~90%),less side reaction and better reaction control.
基金financially supported by the National Natural Science Foundation of China (Nos. 20974074 and 21074078)Natural Science Foundation of Jiangsu Province for Rolling Support Project (BK2011045)+1 种基金a project funded by the PriorityAcademic Program Development of Jiangsu Higher Education Institutions, State Key Lab of Chemical Resource Engineering(Beijing University of Chemical Technology)the Innovation Project of Graduate Students of Jiangsu Province, China(CXZZ11_0091)
文摘Two pH-responsive amphiphilic diblock copolymers, namely polyisobutylene-block-poly[2-（N,N- dimethylamino）ethyl methaerylate] （PIB-b-PDMAEMA） and polyisobutylene-block-poly（metharylic acid） （PIB-b-PMAA）, were synthesized via oxyanion-initiated polymerization, and their multiple self-assembly behaviors have been studied. An exo-01efin-terminated highly reactive polyisobutylene （HRPIB） was first changed to hydroxyl-terminated PIB （PIB-OH） via hydroboration-oxidation of C =C double bond in the chain end, and then reacted with KH to yield a potassium alcoholate of PIB （PIB-O-K＋）. PIB-O-K＋ was immediately used as a macroinitiator to polymerize DMAEMA monomer, resulting in a cationic diblock copolymer PIB-b-PDMAEMA. With the similar synthesis procedure, the anionic diblock copolymer PIB-b- PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate （tBMA） and subsequent hydrolysis of tert-butyl ester groups in PtBMA block. The functional PIB and block copolymers have been fully characterized by 1H-NMR, FT-IR spectroscopy, and gel permeation chromatography （GPC）. These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent. Transmission electron microscopy （TEM） images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles, vesicles with different particle sizes and cylindrical aggregates, depending on various factors including block copolymer composition, solvent polarity and pH value.
基金The authors gratefully acknowledge the support of National Key Research and Development Program of China(2020YFE0204400)National Natural Science Foundation of China(Nos.52090030,52122301,51973191)+3 种基金Shanxi-Zheda Institute of New Materials and Chemical Engineering(2012SZ-FR004)Hundred Talents Program of Zhejiang University(188020*194231701/113)China Postdoctoral Science Foundation(2021M692772)supported by the Fundamental Research Funds for the Central Universities(Nos.2021FZZX001-17).
文摘Eliminating topological defects to achieve monodomain liquid crystals is highly significant for the fundamental studies of soft matter and building long-range ordered materials.However,liquid crystals are metastable and sensitive to external stimuli,such as flow,confinement,and electromagnetic fields,which cause their intrinsic polycrystallinity and topological defects.Here,we achieve the monodomain liquid crystals of graphene oxide over 30 cm through boundary-free sheargraphy.The obtained monodomain liquid crystals exhibit large-area uniform alignment of sheets,which has the same optical polarized angle and intensity.The monodomain liquid crystals provide bidirectionally ordered skeletons,which can be applied as lightweight thermal management materials with bidirectionally high thermal and electrical conductivity.Furthermore,we extend the controllable topology of two-dimensional colloids by introducing singularities and disclinations in monodomain liquid crystals.Topological structures with defect strength from−2 to+2 were realized.This work provides a facile methodology to study the structural order of soft matter at a macroscopic level,facilitating the fabrication of metamaterials with tunable and highly anisotropic architectures.
基金supported by the National Natural Science Foundation of China(Grant No.21776161)。
文摘The bimetallic nanoparticles compositing of Ni-rich core and Cu-rich shell(Ni/Cu NPs)were successfully synthesized by a liquid-phase thermal decomposition method.The content of copper and nickel in Ni/Cu NPs was controllable by adjusting the ratio of two metal precursors,copper formate(Cuf)and nickel acetate tetrahydrate(Ni(OAc)_(2)·4H_(2)O).Ni/Cu NPs were further anchored on graphene oxide(GO)to prepare a magnetic composite catalyst,called Ni/Cu-GO.The dispersibility of Ni/Cu NPs in solution was enhanced by GO anchoring to prevent the sintering and aggregation during the reaction process,thereby ensuring the catalytic and cycling performance of the catalyst.The catalytic transfer hydrogenation(CTH)reaction of nitroaromatics was investigated when ammonia borane was used as the hydrogen source.Cu dominated the main catalytic role in the reaction,while Ni played a synergistic role of catalysis and providing magnetic properties for separation.The Ni_(7)/Cu_(3)-GO catalyst exhibited the best catalytic performance with the conversion and yield of 99%and 96%,respectively,when 2-methyl-5-nitrophenol was used as the substrate.The Ni_(7)/Cu_(3)-GO catalyst also exhibited excellent cyclic catalytic performance with the 5-amino-2-methylphenol yield of above 90%after six cycles.In addition,the Ni_(7)/Cu_(3)-GO catalyst could be quickly recycled by magnetic separation.Moreover,the Ni_(7)/Cu_(3)-GO catalyst showed good catalytic performance for halogen-containing nitroaromatics without dehalogenation.
基金Supported by the National Natural Science Foundation of China (No. 20476072).
文摘It has long been found that the flow pattern of the liquid phase on distillation tray is of great importance on distillation process performance. But until now, there was very few published work on quantitative investigation of this subject. By combining the computational fluid dynamics (CFD) with the mass transfer equation, a theoretical model is proposed for predicting the details of velocity and concentration distributions as well as the tray efficiency of distillation tray column. Using the proposed model, four different cases corresponding to different assumptions of liquid and vapor flowing condition for a distillation tray column were investigated. In Case I, the distributions of velocity and concentration of the incoming liquid from the downcomer and the uprising vapor from the underneath tray spacing are uniform. In Case n, the distribution of the incoming liquid is non-uniform but the uprising vapor is uniform. In Case HI, the distribution of the incoming liquid is uniform but the uprising vapor is non-uniform. In Case IV, the distributions of both the incoming liquid and the uprising vapor are non-uniform. The details of velocity and concentration distributions on a multiple sieve tray distillation column in four different cases were simulated using the proposed model. It is found that the shape of the simulated concentration profiles of vapor and the liquid is quite different from case to case. The computed results also show that the tray efficiency is highly reduced by the maldistribution of velocity and concentration of the incoming liquid and uprising vapor. The tray efficiency for Case I is higher than Case Ⅱ or Case Ⅲ, and that for Case Ⅳ is the lowest. It also reveals that the accumulated effect of maldistribution becomes more pronounced when the number of column trays increased. The present study demonstrates that the use of computational method to predict the mass transfer efficiency for the tray column, especially for the large one, is feasible.
基金the financial supports provided by the National Natural Science Foundation of China (No.21177038)
文摘Two different solvents had been used to separate benzene from 1-hexene under atmosphere pressure by employing one of the following two solvents, viz.: dimethyl sulfoxide (DMSO) at 298.15 K and 318.15 K, and furfural at 298.15 K. A series of liquid-liquid equilibrium (LLE) data had been obtained and the distribution coefficient together with the separation factor were calculated from them. Both the NRTL and the UNIQUAC models could fit in with the experimental data quite well.
基金Supported by the State Key Development Program for Basic Research of China(2003CB615705)
文摘Experimental investigation of the microfiltration （MF） using a revolving cross-flow membrane filter was performed under the condition of constant pressure difference, and different flat membranes made of polyvinylidene fluoride （PVDF, 0.1 μm）, cellulose acetate （CA, 0.22 μm）, sulfonated polyethersulfone （SPES, 0.22 μm） and polyamide （PA, 0.45 μm）, respectively, were used in filtration experiments. The dependence of the filtrate mass of the cross-flow MF on time was measured on-line. The experimental results showed that the effect of the cross-flow on high viscosity medium was more significant than that on the low viscosity one.
基金Supported by the National Natural Science Foundation of China(21476121,21322604)Beijing Natural Science Foundation(2162020)a Foundation for Tsinghua Independent Research Projects(2014z21026)
文摘In this article, a theoretical model for predicting the equilibrium morphology of gas–liquid Janus droplets was built. Based on this model, the effects of bubble radius and volume ratio on morphology change was systematically studied. The increase of bubble radius causes the two parts(bubble and oil drop) in Janus droplets tend to merge while the impact of volume ratio is complicated. When volume ratio increases, these two parts firstly tend to merge, then gradually separate. The accuracy of this model was verified by experimental results.
基金supported by the National Natural Science Foundation of China(No.20674075)Natural ScienceFoundation of Zhejiang Province(No.Y404299)Young Talents Project of Zhejiang Province(No.2008R40G2010065).
文摘The effects of potassium ferricyanide,sodium n-dodecyl sulfate,sodium hydroxide and temperature on the molecular weight and the yield of poly(2,6-dimethyl-1,4-phenylene oxide)(PPO) synthesized in an aqueous medium were studied.It was found that oxygen in air had little influence on the oxidative polymerization of 2,6-dimethylphenol(DMP) in the aqueous medium,and potassium ferricyanide was only an oxidant during the oxidative polymerization of DMP.Sodium n-dodecyl sulfate could stabilize polymer particles an...
基金the National Natural Science Foundation of China(No.20744004 and No.20774025).
文摘As one of the most important catalysts in polyethylene industry,Phillips catalyst(CrO_x/SiO_2)was quite unique for its activation by ethylene monomer without using any activator like alkyl-aluminium or MAO.In this work,the density functional theory(DFT)calculation combined with paired interacting orbitals(PIO)method was applied for the theoretical studies on coordination reaction mechanism between ethylene monomer and two model catalysts namely Cr(Ⅱ)(OH)_2(M1) and silsesquioxane-supported Cr(Ⅱ)(M2)as surfac...
基金financially supported by the National Natural Science Foundation of China(21878169,21991102)the National Key Research and Development Program of China(2019YFA0905100)the Tsinghua University Initiative Scientific Research Program(2018Z05JZY010)。
文摘A mathematical model is developed for the calculation of the nucleation and growth process of silica nanostructured particles prepared by using the drop-by-drop method,and the calculation results of the proposed model is compared with the experimental value obtained from SAXS data.The model provides a non-ideal improvement in the supersaturation calculation and considers the impact of both mass transfer and surface reaction on the particle growth rate.The nucleation and growth rates are coupled depending on the change in monomer concentration over time,based on which the particle size and distribution are calculated.The growth curve of the silica particles from 3 nm to 20 nm and the change in particle number from 0 to over 10^(20) are calculated,which are consistent with the experimental values,establishing the reliability of the model.The calculations of the growth rate reveal that mass transfer controls the growth of silica particles before 10 min and the surface reaction is the rate-determining step after 10 min.The changes in the model parameters obtained by fitting with the SAXS data under different reaction conditions indicate the sensitivity of the corresponding process to different conditions.Moreover,the relationship between the particle growth rate and monomer concentration change is analyzed using the proposed model.
基金the financial support from the National Natural Science Foundation of China(21991104)the Shandong Province Major Science and Technology Innovation Project(2019JZZY020401)。
文摘The methanolysis of amides,which is widely employed in the synthetic organic chemistry,hardly occurs under mild conditions.To safely and controllably intensify the methanolysis reaction with hightemperature and high-pressure environment,a continuous tubular reaction technology is developed,whose space-time yield is over twice of that of the conventional batch reaction.The methanolysis of acetanilide is selected as the representative reaction,and the influences of temperature,pressure,reactant and catalyst concentration,and residence time on the reaction performances are systematically investigated.Taking the advantages of precise temperature and reaction time control by the tubular reactor,the kinetics of acetanilide methanolysis are determined and compared to the kinetics of acetanilide hydrolysis reaction.The tubular reaction method is also employed to test a variety of other amides to show the effects of substituents,steric hindrance,and alkalinity on the reaction rate of methanolysis.
文摘In this article Florian Puchtler at affiliation‘University of Bayreuth’,Josef Breu at affiliation‘University of Bayreuth’,and Ziliang Wu at affiliation‘Zhejiang University’was missing from the author Min Cao,Senping Liu,Qingli Zhu,Ya Wang,Jingyu Ma,Zeshen Li,Dan Chang,Enhui Zhu,Xin Ming,Florian Puchtler,Josef Breu,Ziliang Wu,Yingjun Liu,Yanqiu Jiang,Zhen Xu,Chao Gao list.
