中空纤维支撑液膜萃取Cu(II)的传递性能

The transport of Cu(II) from aqueous solutions containing buffer media through hollow fiber supported liquid membrane (HFSLM) using di(2-ethylhexyl) phosphoric acid (D2EHPA) dissolved in kerosene as membrane phase and hydrochloric acid as striping phase was investigated. A set of factors were studied, including tube side velocity, shell side velocity, pH of the feed phase, Cu(II) concentration in the feed phase, buffer media concentration and D2EHPA concentration in the membrane phase. Experimental results indicate that the mass transfer coefficient increases with increasing both carrier concentration in the organic phase and flow rates on the tube side and shell side, and decreases with increasing initial Cu(II) concentration in the feed phase. With increasing pH value and acetate concentration in the feed phase, the mass transfer coefficient reaches a maximum value then decreases. The optimal operating conditions are obtained at pH value of 4.44 and 0.1 mol&;#8226;L－1 acetic ion concentration in feed phase, and carrier volume fraction of around 10% in kerosene as organic phase. A mathematical model of the transport mechanism through HFSLM is devel-oped. The modeled results agree well with the experimental ones.     

STUDIES OF ADIABATIC FIXED-BED REACTORS (Ⅰ) IGNITION OF REACTORS

An approach for estimating the ignition temperature of adiabatic fixed-bed reactors is suggested. A phase plane of dimensionless temperature and dimensionless concentration is used to show both the ignition and extinction curves of a single catalyst pellet. The trajectory, i. e., the operating line of the reactor, which shows the progress of the chemical reaction, is always a straight line with a slope of —45°. Ignition occurs as the trajectory touches the ignition curve.A simple method is recommended to predict the critical gas inlet temperature which causes reactor ignition without recourse to determining the reaction kinetics. All reactions can be assumed to be of zeroorder.. This assumption introduces negligible error but considerably simplifies the experimental work.     

Absorption of Low Concentration Sulfur Dioxide Using Liquid-containing Microporous Membrane

The absorption of low concentration SO2 in flue gas by using the module of liquid-containing microporous membrane which is made up of hollow fiber and citric acid-sodium citrate buffer solution was investigated. The absorption efficiency of hydrophilic and hydrophobic membranes by using the concept of dynamic contact angle was mainly studied. The influences on absorption efficiency from absorption time, flowrate of gas phase, SO2 concentration of gas phase, air pressure, citrate concentration, pH value of solution as well as the generation of sulfate radical in absorption solution were examined. The results indicate that the hydrophobic hollow fiber membrane is better than hydrophilic membrane, the absorption efficiency decreases with increasing absorption time, gas phase flowrate, gas phase SO2 concentration and air pressure, the absorption rate and capacity of SO2 can be improved by increasing the citrate concentration, the absorption efficiency can be improved by increasing the pH value of citrate solution, the concentration of SO42- in absorption solution increases linearly with the absorption time at a rate around 0.192 g/(L×h).     

Numerical Simulation on Gas-Solid Two-Phase Turbulent Flow in FCC Riser Reactors(Ⅱ) Numerical Simulation on the Gas-Solid Two-Phase Turbulent Flow

Numerical simulation on the flow,heat transfer and cracking reactions in commercial fluid catalyticcracking(FCC)riser reactors were carried out employing the developed turbulent gas-solid two-phase flow-reac-tion model for FCC riser reactors given in Part Ⅰ of the present paper.Detailed information about the turbulentflow fields in the riser reactor obtained revealed the basic characteristics of the gas-solid two-phase turbulentflows when heat transfer and catalytic cracking reactions were co-existing in the riser.Results showed that thedistributions of the flow,the turbulence kinetic energy and the catalyst particle concentration are not uniform inthe axial,radial and tangential directions.The most complicated part of the riser reactor is the feed injectingzone.The complicated configuration of the turbulent gas-solid two-phase flows would exert a great influence onthe results of interphase heat transfer and cracking reactions.     

RESIDENCE TIME DISTRIBUTION IN AN OPEN REACTOR:EFFECT OF BACKGROUND REACTANT ON TRACER DISPERSION

A new approach is presented for deriving the residence time distribution(RTD)in open-type reactors with exclusion of residence in the fore section.Inasmuch as failure to predict the con-version of chemical reactions has been evidenced in many occasions,numerical solution of tracerdispersion in the presence of background concentration gradient of reactant is given to demonstratethe strong effect of background reactant on the true RTD a reactant molecule experiences.Withinthe error of computation,the conversion of a first-order chemical reaction under steady state is shownto be equal in both closed and open reactors,despite difference in relevant RTDs     

Numerical Simulation on Gas-Solid Two-Phase Turbulent Flow in FCC Riser Reactors (II) Numerical Simulation on the Gas-Solid Two-Phase Turbulent Flow

Numerical simulation on the flow, heat transfer and cracking reactions in commercial fluid catalytic cracking(FCC)riser reactors were carried out employingthe developed turbulent gas-solid two-phase flow-reaction model for FCC riser reactors given in Part Ⅰ of thepresent paper.Detailed information about the turbulentflow fields in the riser reactor obtained revealed the basic characteristics of the gas-solid two-phase turbulent flows when heat transfer and catalytic cracking reactions were co-existing in the riser. Results showed that the distributions of the flow, the turbulence kinetic energy and the catalyst particle concentration arenot uniform in the axial, radial and tangential directions. The most complicated part of the riser reactor is the feed injecting zone. The complicated configuration of the turbulent gas-solid two-phase flows would exert a great influence on the results of interphase heat transfer and cracking reactions.     

NO_x Absorption in Full Scale Plant Columns with Structured Packings

A mathematical model of nitrogen oxide(NO_x)absorption is adopted and solved for adiabatic operation of a column with structured packings on the basis of the film theory.Removal rate,outlet concentration,oxidation degree of NO_x and outlet acid concentration,liquid acid temperature are simulated and tested.The gas phase reactions and equilibria,gas phase mass transfer,interracial equilibria,and liquid phase reactions are considered in the model.Absorption of nitrogen oxides is studied in packed with Mellapak 250Y columns in series in an industrial process of 20000 t oxalic acid per year.Favorable agreement is shown between the model predictions and the on-site observations.     

规整填料塔吸收NOx过程的模拟和实验研究

A mathematical model of nitrogen oxide （NOx） absorption is adopted and solved for adiabatic operation of a column with structured packings on the basis of the film theory. Removal rate, outlet concentration, oxidation degree of NOx and outlet acid concentration, liquid acid temperature are simulated and tested. The gas phase reactions and equilibria, gas phase mass transfer, interracial equilibria, and liquid phase reactions are considered in the model. Absorption of nitrogen oxides is studied in packed with Mellapak 250Y columns in series in an industrial process of 20000 t oxalic acid per year. Favorable agreement is shown between the model predictions and the on-site observations.     

催化裂化提升管反应器中颗粒聚团裂化反应的数值模拟

Behavior of catalytic cracking reactions of particle cluster in fluid catalytic cracking (FCC) riser reactors was numerically analyzed using a four-lump mathematical model. Effects of the cluster porosity, inlet gas velocity and temperature, and coke deposition on cracking reactions of the cluster were investigated. Distributions of temperature, gases, and gasoline from both catalyst particle cluster and an isolated catalyst particle are presented. The reaction rates from vacuum gas oil (VGO) to gasoline, gas and coke of individual particle in the cluster are higher than those of the isolated particle, but it reverses for the reaction rates from gasoline to gas and coke. Less gasoline is produced by particle clustering. Simulated results show that the produced mass fluxes of gas and gasoline increase with the operating temperature and molar concentration of VGO, and decrease due to the formation of coke.     

DYNAMIC ANALYSIS OF GAS STRIPPING DURING ETHANOL FERMENTATION IN CSTR

1 INTRODUCTIONInhibition phenomena have frequently been observed in microbial reactions.When thesubstrate concentration in the broth is high enough,the contour curve of the specificgrowth rate of cells is no longer monotonically increasing in a substrate-product phaseplane.The system exhibits a substrate inhibition.Some supersession products can affectthe growth and the yield of the cells as well as the viability of the microorganisms.Forexample,in the case of using Saccharomyces,the ethanol product inhibits the growth     

以聚苯乙烯为模板制备有序大孔氧化铝

采用少皂乳液聚合法成功制备了单分散的聚苯乙烯微球,以微球自组装后的聚苯乙烯胶体晶体为大孔模板,铝溶胶为前驱体填充模板,干燥焙烧除去模板后制备了氧化铝载体。用激光粒度仪、扫描电镜、X射线衍射和氮气吸脱附对聚苯乙烯胶体晶体和氧化铝载体进行了表征。结果表明:少皂乳液聚合法制备的聚苯乙烯微球具有粒径较小(100~350 nm)、单分散性好(0.005)、收率高(约80%)等优点;自组装的胶体晶体呈规则有序排列,微球表面光滑洁净,并以此为模板成功制备了具有三维有序结构的、大孔孔径可调的氧化铝材料。     

Fabrication & characterization of macroporous CdSe nanostructure via colloidal crystal templating with electrodeposition method

Large area ordered arrays of macroporous Cadmium Selenide (CdSe) nanostructure, which possesses high refractive index and negligible absorption in the visible spectrum critical for the realization of photonic band gaps, was prepared via colloidal templating by galvanostatic electrodeposition. This work investigates the effect of electrodeposition parameters on the macroporous CdSe nanostructure. Field Emission Scanning Electron Microscope (FESEM) images showed two and three dimensional porous structures, consisting of interconnected close-packed arrays of pores. For CdSe thin film of thickness less than 1/3 of the diameter of a polystyrene sphere, it showed a monolayer of circular pores. As for film thickness close to the diameter of the sphere, the pores adopted irregular rounded triangular shapes. When the film thickness was more than one layer of the colloidal polystyrene template, the pores were spherical and had the same diameter as the polystyrene spheres. X-ray Diffraction (XRD) showed that the CdSe films prepared had a cubic structure with nanometer grain size, which was smaller than the diameter of the template spheres as well as the diameter of the interconnected channels. A range of 45–70 nm thick CdSe films with > 90% optical transmittance showed that there was negligible absorption at wavelength of 750 nm. In addition, the CdSe thin film exhibited a band gap energy of 2.07 eV, blue-shifted from the characteristic 1.7 eV of CdSe. This blue-shift characteristic of the deposited CdSe film further indicated that it was nanocrystalline which is potentially useful in photonic applications.     

LiMn2O4空心多孔正极材料的制备

以水热法所制碳球为模板,采用溶胶?凝胶法制备LiMn2O4空心多孔颗粒(PLMO),研究了煅烧温度和碳球加入量对样品相演化和表面形貌的影响,比较了PLMO和未加入碳球的LiMn2O4 (LMO)的电化学性能. 结果表明,650?750℃煅烧12 h可制得蜂窝状孔型结构的PLMO;在放电倍率0.5C下循环50次,PLMO的放电容量从126 mA?h/g降至111 mA?h/g,均高于相应LMO的放电容量. 在5C放电倍率下,PLMO的首次放电容量可达89 mA?h/g,较LMO提高约39%.     

Preparation and Characterization of SiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> Core–Shell Microspheres as RP-HPLC Stationary Phase

Novel SiO₂/SiO₂ core–shell monodisperse silica spheres for high-performance liquid chromatography packing materials are prepared by the layer-by-layer self-assembly technique. The core–shell silica spheres consist of micrometer-sized porous silica spheres as the core and a thin mesoporous silica shell formed from multilayer nanometer-sized silica particles. In addition, a reversed-phase packing by bonding octadecyltrichlorosilane on SiO₂/SiO₂ particles through alkyl-modified method is prepared and characterized. The results show that the carbon content of the new reversed-phase stationary phase increases by approximately 45% compared with the uncoated octadecyl-bonded SiO₂ stationary phase. Eight kinds of tested aromatic compounds are well-separated on the packing and the peaks are symmetrical, which demonstrates that the packing acts as an excellent reversed-phase chromatographic stationary phase.     

Synthesis and characterization of air‐stable magnetic Fe composites microspheres of narrow size distribution

Air‐stable Fe magnetic nanoparticles entrapped within carbon and porous crosslinked polystyrene microspheres of narrow size distribution were prepared by the following sequential steps: (1) Polystyrene/poly(divinyl benzene) and polystyrene/poly(styrene‐divinyl benzene) uniform micrometer‐sized composite particles were prepared by a single‐step swelling of uniform polystyrene template microspheres dispersed in an aqueous continuous phase with emulsion droplets of dibutyl phthalate containing the monomers divinyl benzene and styrene and the initiator benzoyl peroxide. The monomers within the swollen polystyrene template microspheres were then polymerized by raising the temperature to 73°C; (2) Porous poly (divinyl benzene) and poly(styrene‐divinyl benzene) uniform crosslinked microspheres were prepared by dissolution of the polystyrene template part of the former composite particles; (3) Uniform magnetic poly(divinyl benzene)/Fe and poly(styrene‐divinyl benzene)/Fe composite microspheres were prepared by entrapping Fe(CO)₅ within the porous crosslinked microspheres, by suction of the Fe complex into the dried porous particles, followed by decomposition of the encapsulated Fe(CO)₅ at 200°C in Ar atmosphere; (4) Uniform magnetic air‐stable C/Fe composite microspheres were prepared similarly, apart from changing the decomposition temperature from 200 to 600°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fabrication & characterization of macroporous CdSe nanostructure via colloidal crystal templating with electrodeposition method

Large area ordered arrays of macroporous Cadmium Selenide (CdSe) nanostructure, which possesses high refractive index and negligible absorption in the visible spectrum critical for the realization of photonic band gaps, was prepared via colloidal templating by galvanostatic electrodeposition. This work investigates the effect of electrodeposition parameters on the macroporous CdSe nanostructure. Field Emission Scanning Electron Microscope (FESEM) images showed two and three dimensional porous structures, consisting of interconnected close-packed arrays of pores. For CdSe thin film of thickness less than 1/3 of the diameter of a polystyrene sphere, it showed a monolayer of circular pores. As for film thickness close to the diameter of the sphere, the pores adopted irregular rounded triangular shapes. When the film thickness was more than one layer of the colloidal polystyrene template, the pores were spherical and had the same diameter as the polystyrene spheres. X-ray Diffraction (XRD) showed that the CdSe films prepared had a cubic structure with nanometer grain size, which was smaller than the diameter of the template spheres as well as the diameter of the interconnected channels. A range of 45–70 nm thick CdSe films with > 90% optical transmittance showed that there was negligible absorption at wavelength of 750 nm. In addition, the CdSe thin film exhibited a band gap energy of 2.07 eV, blue-shifted from the characteristic 1.7 eV of CdSe. This blue-shift characteristic of the deposited CdSe film further indicated that it was nanocrystalline which is potentially useful in photonic applications.     

Functionalization of Tailored Porous Carbon Monolith for Decontamination of Radioactive Substances

As the control over radioactive species becomes critical for the contemporary human life, the development of functional materials for decontamination of radioactive substances has also become important. In this work, a three-dimensional (3D) porous carbon monolith functionalized with Prussian blue particles was prepared through removal of colloidal silica particles from exfoliated graphene/silica composite precursors. The colloidal silica particles with a narrow size distribution were used to act a role of hard template and provide a sufficient surface area that could accommodate potentially hazardous radioactive substances by adsorption. The unique surface and pore structure of the functionalized porous carbon monolith was examined using electron microscopy and energy-dispersive X-ray analysis (EDS). The effective incorporation of PB nanoparticles was confirmed using diverse instrumentations such as X-ray diffraction (XRD), Fourier-transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS). A nitrogen adsorption/desorption study showed that surface area and pore volume increased significantly compared with the starting precursor. Adsorption tests were performed with ¹³³Cs ions to examine adsorption isotherms using both Langmuir and Freundlich isotherms. In addition, adsorption kinetics were also investigated and parameters were calculated. The functionalized porous carbon monolith showed a relatively higher adsorption capacity than that of pristine porous carbon monolith and the bulk PB to most radioactive ions such as ¹³³Cs, ⁸⁵Rb, ¹³⁸Ba, ⁸⁸Sr, ¹⁴⁰Ce, and ²⁰⁵Tl. This material can be used for decontamination in expanded application fields.     

三维有序大孔氧化钇稳定氧化锆的制备与表征

以聚苯乙烯(polystyrene, PS)胶体晶体为模板,采用柠檬酸凝胶方法制备氧化钇稳定氧化锆(yttria stabilized zirconia, YSZ)前驱体溶胶,采用浸渍-提拉方法向PS模板的空隙中填充YSZ溶胶,煅烧去除模板后成功地制备了三维有序大孔YSZ材料.研究前驱体溶胶不同浓度、浸渍次数以及煅烧条件等因素对大孔YSZ结构的影响.用扫描电子显微镜对YSZ的微观结构进行表征.结果表明:前驱体溶胶的浓度在0.3～0.4 mol/L的范围内,浸渍次数为1次或2次,煅烧温度为600℃时可以得到高度有序的大孔YSZ.     

Monodispersed nanoporous starburst carbon spheres and their three-dimensionally ordered arrays

Controlled syntheses of highly monodispersed nanoporous carbon spheres via a nanocasting route are described. Previously reported monodispersed super-microporous or mesoporous silica spheres with hexagonally ordered pore channels were used as sacrificial templates, and the effect of pore sizes of the templates on the porous properties of the nanocast carbon spheres was comprehensively studied. The resultant carbon spheres exhibited a unique starburst structure derived from radially-aligned pore channels in the silica template, and had a BET surface area of over 1000 m²g^?1. It was found out that the radial alignment and sufficiently large pore size of hexagonally ordered pore channels in the silica spheres were effective to enhance the degree of order of the starburst structure in the nanocast carbon spheres and that ordered nanoporous carbon spheres could be obtained even from the MCM-41-type mesoporous silica. The diameters of the nanoporous carbon spheres were controlled in the sub-micrometer range by changing the sizes of silica templates. Furthermore, three-dimensionally ordered arrays consisting of nanoporous carbon spheres were successfully fabricated via the self-assembly of mesoporous silica/carbon composite spheres and the subsequent dissolution of the silica templates.     

Preparation Method for Ruthenium Catalysts Supported by Carbon‐Coated Aluminum Foams

A preparation method is proposed for coating aluminum and aluminum alloy foams with a porous carbon layer for application as a catalyst support. The polymerization of furfuryl alcohol with diluted oxalic acid was used as precursor for the carbon layer. The polymer layer was distributed by applying centrifugal forces via spinning foam substrates during the polymerization process to prevent clogging and for homogeneous growth of the polymer layer. A homogeneous deposition precipitation method was applied for incorporation of ruthenium on carbon‐coated foam substrates. The carbon coating was characterized by X‐ray tomography to measure the thickness distribution. The specific surface and pore volume distribution were determined by gas adsorption (BET) and mercury porosimetry. The prepared Ru/C foam catalysts were adopted as a stirrer in a rotating foam reactor for hydrogenation of glucose, a simple biomass model substance.