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SCI和EI收录∣中国化工学会会刊
本期目录
2012年 第20卷 第5期 刊出日期:2012-10-28
    Adsorption and Desorption of Praseodymium (Ⅲ) from Aqueous Solution Using D72 Resin
    熊春华, 朱京妃, 沈忱, 陈青
    Chinese Journal of Chemical Engineering. 2012, 20(5):  823-830. 
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    In this work, the feasibility of using a macroporous strong acid ion exchange resin (D72) as an adsorbent for praseodymium (Ⅲ) was examined. The adsorption behavior and mechanism were investigated with various chemical methods and IR spectrometry. The results showed that the loading of Pr (Ⅲ) ions was strongly dependent on pH of the medium and the optimal adsorption condition is in HAc-NaAc medium with pH value of 3.0. Adsorption kinetics of Pr (Ⅲ) ions onto D72 resin could be best described by pseudo-second-order model. The maximum adsorption capacity of D72 for Pr (Ⅲ) was evaluated to be 294 mg·g-1 for the Langmuir model at 298K. The apparent activation energy, Ea, was 14.71 kJ·mol-1. The calculated data of thermodynamic parameters, ΔSΘ value of 100 J·mol-1·K-1 and ΔHΘ value of 8.89 kJ·mol-1, indicate the endothermic nature of the adsorption process, while a decrease of ΔGΘ with increasing temperature indicates the spontaneous nature of the adsorption process. Finally, Pr (Ⅲ) can be eluted by using 1.00 mol·L-1 HCl-0.50 mol·L-1 NaCl solution and the D72 resin can be regenerated and reused. Thomas model was successfully applied to experimental data to predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design. The characterization before and after adsorption of Pr (Ⅲ) ions on D72 resin was conformed by IR.
    Recovery of Tungsten (Ⅵ) from Aqueous Solutions by Complexation-ultrafiltration Process with the Help of Polyquaternium
    曾坚贤, 孙霞辉, 郑立锋, 贺勤程, 李书
    Chinese Journal of Chemical Engineering. 2012, 20(5):  831-836. 
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    Polyquaternium-6 (PQ6) as the water-soluble polymer was used for complexing the anion forms of tungsten (Ⅵ) before ultrafiltration. Tungsten (Ⅵ)-PQ6 complex was retained by polysulfone hollow fiber ultrafiltration membrane in the complexation-ultrafiltration process. Effects of various operating parameters such as polymer metal ratio(PMR), pH and chloride ion concentration on permeate flux (J) and tungsten rejection coefficient (R) were investigated. The integration of four experiments including concentration, decomplexation, diafiltration and reuse of regenerated polymer was carried out. In the process of concentration, J declines slowly and R is about 1 at PMR of 3 and pH of 7. Tungsten concentration in the retentate increases linearly with volume concentration factor. Tungsten is concentrated efficiently with the membrane. The concentrated retentate was used further for the decomplexation. It takes about 6 min to reach the decomplexation equilibrium at chloride ion concentration of 50 mg·L-1. The decomplexation percentage of tungsten (Ⅵ)-PQ6 complex reaches 56.1%. In the diafiltration process, tungsten (Ⅵ) can be extracted effectively by using 50 mg·L-1 chloride ion solution, and the purification of the regenerated PQ6 is acceptably satisfactory. The regenerated PQ6 was used to bind tungsten (Ⅵ) at various pH values. The binding capacity of the regenerated PQ6 is close to that of fresh PQ6, and the recovery percentage of binding capacity is higher than 90%.
    Continuous Separation of Cesium Based on NiHCF/PTCF Electrode by Electrochemically Switched Ion Exchange
    孙斌, 郝晓刚, 王忠德, 张忠林, 刘世斌, 官国清
    Chinese Journal of Chemical Engineering. 2012, 20(5):  837-842. 
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    Nickel hexacyanoferrate (NiHCF) film was synthesized on porous three-dimensional carbon felt (PTCF) substrate by repetitious batch chemical depositions, and the NiHCF/PTCF electrode was used as electrochemically switched ion exchange (ESIX) electrode in a packed bed for continuous separation for cesium ions. The morphologies of the prepared electrodes were characterized by scanning electron microscopy and the effects of solution concentration on the ion-exchange capacity of the electrodes were investigated by cyclic voltammetry technique. Cycling stability and long-term storage stability of NiHCF/PTCF electrodes were also studied. The NiHCF/PTCF electrodes with excellent ion-exchange ability were used to assemble a diaphragm-isolated ESIX reactor for cesium separation. Continuous separation of cesium and regeneration of NiHCF/PTCF electrode based on the diaphragm-isolated reactor were performed in a laboratory-scale two-electrode system.
    Reactive Extraction of Nicotinic Acid with Trialkylamine in n-Octanol
    李德亮, 于飞, 常志显
    Chinese Journal of Chemical Engineering. 2012, 20(5):  843-848. 
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    The distributions of nicotinic acid (NA) between water and trialkylamine (N235) dissolved in n-octanol was studied. The complexes of N235 and NA were investigated by Fourier transformation infrared spectrometry to deduce the reaction mechanism. It was found that N235/n-octanol was an efficient extractant for extracting nicotinic acid. The favorable operation conditions were equilibrium aqueous pH 4.2 to 5.5 and initial N235 concentration<0.42 mol·L-1. The reaction processes included the reaction between neutral N235 and neutral NA and the reaction between protonated N235 and anionic NA. Based on the mass action law and some assumptions, an expression for distribution coefficient D was proposed. The apparent extraction equilibrium constants were calculated by fitting the experimental data and the results were satisfactory.
    CO2 Capture by Vacuum Swing Adsorption Using F200 and Sorbead WS as Protective Pre-layers
    徐冬, Penny Xiao, 李刚, 张军, Paul Webley, 翟玉春
    Chinese Journal of Chemical Engineering. 2012, 20(5):  849-855. 
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    In order to solve the water issues when 13X zeolite was applied to capture CO2 from wet flue gas by vacuum swing adsorption process, multi-layered adsorption system was considered regarding activated alumina F200 and silica gel based Sorbead WS as pre-layer materials. LBET (extended Largmuir-BET) model and extended CMMS (cooperative multimolecular sorption) equation were simulated respectively to describe water loading on F200 and Sorbead WS. The two equations can be well added into our in-house simulator to simulate double-layered CO2-VSA (vacuum swing adsorption) process. Results indicated that water can be successfully stopped in pre-layers with a good CO2 capture performance.
    Effects of Geometric Configurations on the Performance of Reverse Flow Diverters in Reverse Flow Mode
    徐聪
    Chinese Journal of Chemical Engineering. 2012, 20(5):  856-862. 
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    The reverse flow diverter (RFD) consisting of a nozzle and a diffuser is a key component in pneumatic pulse jet pumps. We investigated the effects of suction gap and diffuser configurations on RFD performance during the reverse flow mode. Three suction gap configurations were examined: (1) an axisymmetrical cylinder, (2) a cuboid whose bottom plane had no half-circle groove and was level with the diffuser entrance lower border, and (3) a cuboid with a half-circle groove on the bottom plane. Among them, the second one resulted in the highest RFD pumping capacity. The effect of receiver presence before the diffuser was also examined. RFD pumping efficiency was found to be enhanced in the presence of a receiver before the diffuser when the suction gap length is small and the jet outlet velocity at the nozzle exit is high enough. Based on experimental data, a dimensionless performance curve of the suction factor q versus the ratio of Euler numbers in sections out-out and 0-0 Euout/Eu0 was derived. This curve is insensitive to suction gap configurations.
    Heat Transfer Behavior in a Square Duct with Tandem Wire Coil Element Insert
    Smith Eiamsa-ard, Narin Koolnapadol, Pongjet Promvonge
    Chinese Journal of Chemical Engineering. 2012, 20(5):  863-869. 
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    Effects of insertion of tandem wire coil elements used as turbulator on heat transfer and turbulent flow friction characteristics in a uniform heat-flux square duct are experimentally investigated in this work. The experiment is conducted for turbulent flow with the Reynolds number from 4000 to 25000. The wire coil element is inserted into the duct with a view to generating a swirl flow that assists to wash up the flow trapped in the duct corners and then increase the heat transfer rate of the test duct. Apart from the full-length coil, 1D and 2D length coil elements placed in tandem inside the duct with various free-space lengths are introduced to reduce the friction loss. The results obtained from these wire coil element inserts are also compared with those from the smooth duct. The experimental results reveal that the use of wire coil inserts for the full-length coil, 1D and 2D coil elements with a short free-space length leads to a considerable increase in heat transfer and friction loss over the smooth duct with no insert. The full-length wire coil provides higher heat transfer and friction factor than the tandem wire coil elements under the same operating conditions. Also, performance evaluation criteria to assess the real benefits in using the wire coil insert into the square duct are determined.
    Testing for Nonlinearity in Dynamic Characteristics of Vertical Upward Oil-Gas-Water Three-phase Bubble and Slug Flows
    朱雷, 金宁德, 高忠科, 杜萌, 王振亚
    Chinese Journal of Chemical Engineering. 2012, 20(5):  870-882. 
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    Based on the conductance fluctuation signals measured from vertical upward oil-gas-water three-phase flow experiment, time frequency representation and surrogate data method were used to investigate dynamical characteristics of oil-in-water type bubble and slug flows. The results indicate that oil-in-water type bubble flow will turn to deterministic motion with the increase of oil phase fraction fo and superficial gas velocity Usg under fixed flowrate of oil-water mixture Qmix. The dynamics of oil-in-water type slug flow becomes more complex with the increase of Usg under fixed flowrate of oil-water mixture. The change of fo leads to irregular influence on the dynamics of slug flow. These interesting findings suggest that the surrogate data method can be a faithful tool for characterizing dynamic characteristics of oil-in-water type bubble and slug flows.
    Turbulent Characteristic of Liquid Around a Chain of Bubbles in Non-Newtonian Fluid
    李少白, 马友光, 朱春英, 付涛涛, 李怀志
    Chinese Journal of Chemical Engineering. 2012, 20(5):  883-888. 
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    The turbulence behavior of gas-liquid two-phase flow plays an important role in heat transfer and mass transfer in many chemical processes. In this work, a 2D particle image velocimetry (PIV) was used to investigate the turbulent characteristic of fluid induced by a chain of bubbles rising in Newtonian and non-Newtonian fluids. The instantaneous flow field, turbulent kinetic energy (TKE) and TKE dissipation rate were measured. The results demonstrated that the TKE profiles were almost symmetrical along the column center and showed higher values in the central region of the column. The TKE was enhanced with the increase of gas flow and decrease of liquid viscosity. The maximum TKE dissipation rate appeared on both sides of the bubble chain, and increased with the increase of gas flow rate or liquid viscosity. These results provide an understanding for gas-liquid mass transfer in non-Newtonian fluids.
    AmmAmmoximation of Cyclohexanone to Cyclohexanone Oxime Catalyzed by Titanium Silicalite-1 Zeolite in Three-phase System*
    刘国清, 吴剑, 罗和安
    Chinese Journal of Chemical Engineering. 2012, 20(5):  889-894. 
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    An innovative green process of producing ε-caprolactam was proposed by integrating ammoximation and Beckmann rearrangement effectively. As a first part of the new process, TS-1 molecular sieve-catalyzed synthesis of cyclohexanone oxime from cyclohexanone, ammonia and hydrogen peroxide was carried out in a batch plant. Cyclohexane was used as the solvent in the three-phase reaction system. The influences of essential process parameters on ammoximation were investigated. Under the reaction conditions as catalyst content of 2.5% (by mass); H2O2/yclohexanone molar ratio of 1.10; NH3/cyclohexanone molar ratio of 2.20; reaction temperature of 343 K; reaction time of 5 h, high conversion of cyclohexanone and selectivity to oxime (both>99%) were obtained. Thus, the three-phase ammoximation process showed equal catalytic activity as TS-1 but much more convenient and simpler for the separation of catalyst in comparison to the industrial two-phase system with t-butanol used as solvent.
    Photocatalytic Degradation of Methylene Blue with Side-glowing Optical Fiber Deliverying Visible Light
    储金宇, 仲蕾
    Chinese Journal of Chemical Engineering. 2012, 20(5):  895-899. 
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    The side-glowing optical fibers (SOFs) were chosen as the conducting medium of endogenous light; and 20 mg·L-1 methylene blue was chosen as the target to be degraded. The SOF is made up of quartz core with a silicon cladding, which can emit light through side surface more uniformly and transmit light for longer distance to avoid attenuation of light by liquid medium. The filament lamp was chosen as visible light source. Different reaction conditions, such as the presence of optical fiber or not, the quantity of SOF, light irradiation intensity were tested by measuring the methylene blue degradation of methylene blue. The results show that suitable reaction conditions were 1.167 g·L-1 Ag+/TiO2 with 7% (by mass) of Ag+ doped in TiO2, and 500 roots of SOF (30 cm length in solution). The photocatalytic degradation efficiency under 300W lamp irradiation for 8h was about 97%. And the photocatalytic degradation efficiency of methylene blue degradation was proportional to SOF quantity, light irradiation intensity and catalytic dosage within a certain range. Compared with general UV and visible light SOFs could save a huge amount of energy and cost, in the potential applications in dealing with organic pollutants on a large scale.
    Characterization and Catalytic Properties of Al-MCM-41 Mesoporous Materials Grafted with Tributyltin Chloride*
    宋伟明, 刘星, 荆涛, 邓启刚
    Chinese Journal of Chemical Engineering. 2012, 20(5):  900-905. 
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    Surface organometallic chemistry (SOMC) is a recently developing research field. It is of great significance for the quantitative modification, restoration of solid surface, identification of the physical and chemical nature of surface and the preparation of new catalyst. The production of R3Snl-O-MCM-41 (R3SnlM) was obtained by heating tributyltin chloride and Al-MCM-41 mixture at 170℃ for 5 h under stirring in nitrogen atmosphere. The composition, structure and surface physical and chemical properties of the samples were characterized by inductively coupled plasma mass spectrometry (ICP-MS), 13C, 119Sn, 29SI and 27Al solid state NMR (nuclear magnetic resonance) spectra, in-situ pyridine infrared spectroscopy (Py-IR), N2 adsorption-desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), etc. The results of ICP and organic elemental analysis shows that the grafting yield wSn was 6.46% for R3SnlM. H0 (the negative logarithm of the acid concentration)and the number of acid sites for R3SnlM respectively were 2.77-0.99 and 4.8 mmol·g-1 by the Hammett method. N2 adsorption-desorption, XRD, TEM analysis showed that R3SnlM with ordered hexagonal mesopore structure, resulted in the decease of surface areas and pore size as well as the increase of mesoporous volume and surface acidity, as compared to Al-MCM-41. R3SnlM was used in the synthesis of isoamyl acetate. The yield of isoamyl acetate was 96% when n(isoamyl alcohol):n(acetic acid) 1.0:1.0,wR3SnM 5%, 138℃ for 5 h. The catalyst can be reused and the yield of 86% can be attained when catalyst was reused five times at the same catalytic conditions.
    Direct Synthesis of Dimethyl Carbonate from CO2 and CH3OH Using 0.4nm Molecular Sieve Supported Cu-Ni Bimetal Catalyst*
    陈惠玲, 王栓紧, 肖敏, 韩冬梅, 卢一新, 孟跃中
    Chinese Journal of Chemical Engineering. 2012, 20(5):  906-913. 
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    The 0.4 nm molecular sieve supported Cu-Ni bimetal catalysts for direct synthesis of dimethyl carbonate (DMC) from CO2 and CH3OH were prepared and investigated. The synthesized catalysts were fully characterized by BET, XRD (X-ray diffraction), TPR (temperature programmed reduction), IR (infra-red adsorption), NH3-TPD (temperature programmed desorption) and CO2-TPD (temperature programmed desorption) techniques. The results showed that the surface area of catalysts decreased with increasing metal content, and the metals as well as Cu-Ni alloy co-existed on the reduced catalyst surface. There existed interaction between metal and carrier, and moreover, metal particles affected obviously the acidity and basicity of carrier. The large amount of basic sites facilitated the activation of methanol to methoxyl species and their subsequent reaction with activated carbon dioxide. The catalysts were evaluated in a continuous tubular fixed-bed micro-gaseous reactor and the catalyst with bimetal loading of 20% (by mass) had best catalytic activities. Under the conditions of 393 K, 1.1 MPa, 5 h and gas space velocity of 510 h-1, the selectivity and yield of DMC were higher than 86.0% and 5.0%, respectively.
    Numerical Study on Laminar Burning Velocity and Flame Stability of Premixed Methane/Ethylene/Air Flames*
    陈珊珊, 蒋勇, 邱榕, 安江涛
    Chinese Journal of Chemical Engineering. 2012, 20(5):  914-922. 
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    A numerical study on premixed methane/ethylene/air flames with various ethylene fractions and equivalence ratios was conducted at room temperature and atmospheric pressure. The effects of ethylene addition on laminar burning velocity, flame structure and flame stability under the condition of lean burning were investigated. The results show that the laminar burning velocity increases with ethylene fraction, especially at a large equivalence ratio. More ethylene addition gives rise to higher concentrations of H, O and OH radicals in the flame, which significantly promotes chemical reactions, and a linear correlation exists between the laminar burning velocity and the maximum H+OH concentration in the reaction zone. With the increase of ethylene fraction, the adiabatic flame temperature is raised, while the inner layer temperature becomes lower, contributing to the enhancement of combustion. Markstein length and Markstein number, representative of the flame stability, increase as more ethylene is added, indicating the tendency of flame stability to improve with ethylene addition.
    One Step Bioleaching of Sulphide Ore with Low Concentration of Arsenic by Aspergillus niger and Taguchi Orthogonal Array Optimization*
    Sadia Ilyas, 池汝安, Jae Chun Lee, Haq Nawaz Bhatti
    Chinese Journal of Chemical Engineering. 2012, 20(5):  923-929. 
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    A study was carried out to examine the possibility for Aspergillus niger strain KBS4 to bioleach metals from sulphide ore with low concentration of arsenic and to optimize the parameters that affect this process by orthogonal array optimization. Fungal sample was collected, purified and sequenced. The bioleaching process was optimized with L25 Taguchi orthogonal experimental array design. Five factors were investigated and 25 batch bioleaching tests were run at five levels for each factor. The parameters were initial pH, particle size, pulp density, initial inoculums and residence time for bioleaching. The experimental results showed that under optimized leaching conditions: pH 5.5, particle size 180 μm, initial inoculums size 3×107 spores per ml, pulp density 15% and residence time of 20 days, the bioleach ability of metals were 63% Fe, 68% Zn, 60% As, 79% Cu and 54% Al. The biosorption of metal ions by fungal biomass might occur during the bioleaching process but it did not hinder the removal of metal ions by bioleaching.
    Optimizing the Chemical Compositions of Protective Agents for Freeze-drying Bifidobacterium longum BIOMA 5920*
    杨婵媛, 朱晓丽, 范代娣, 米钰, 骆艳娥, 惠俊峰, 苏然
    Chinese Journal of Chemical Engineering. 2012, 20(5):  930-936. 
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    Freeze drying has a deleterious effect on the viability of microorganisms. In front of this difficulty, the present study adopts response surface methodology to optimize the chemical compositions of protective agents to seek for maximum viability of Bifidobacterium longum BIOMA 5920 during freeze-drying. Through the comparative analysis of single protectant, the complex protective agents show better effect on the Bifidobacterium viability. Human-like collagen (HLC), trehalose and glycerol are confirmed as significant factors by Box-Behnken Design. The optimized formula for these three variables is tested as follows: HLC 1.23%, trehalose 11.50% and glycerol 4.65%. Under this formula, the viability is 88.23%, 39.67% higher in comparison to the control. The viable count is 1.07×109 cfu·g-1, greatly exceeding the minimum viable count requirement (106cfu·g-1).
    Solubilities of Nizatidine in Methanol+Water, Ethanol+Water and i-Propanol+Water from 273.15 to 303.15 K*
    李音, 吕秀阳
    Chinese Journal of Chemical Engineering. 2012, 20(5):  937-941. 
    摘要 ( )   PDF (204KB) ( )  
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    The solubilities of nizatidine in methanol+water, ethanol+water and i-propanol+water mixtures were determined in the temperature range from 273.15 K to 303.15 K at atmospheric pressure by a static analytical method. The general single model was used to correlate the experimental data, which fits the data very well.
    Effect of Propanoic Acid on Ethanol Fermentation by Saccharomyces cerevisiae in an Ethanol-Methane Coupled Fermentation Process*
    张成明, 杜风光, 王欣, 毛忠贵, 孙沛勇, 唐蕾, 张建华
    Chinese Journal of Chemical Engineering. 2012, 20(5):  942-949. 
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    Propanoic acid accumulated in an ethanol-methane coupled fermentation process affects the ethanol fermentation by Saccharomyces cerevisiae. The effects of propanoic acid on ethanol production were examined in cassava mash under different pH conditions. Final ethanol concentrations increased when undissociated propanoic acid was <30.0 mmol·L-1. Propanoic acid, however, stimulated ethanol production, as much as 7.6% under proper conditions, but ethanol fermentation was completely inhibited when undissociated acid was >53.2 mmol·L-1. Therefore, the potential inhibitory effect of propanoic acid on ethanol fermentation may be avoided by controlling the undissociated acid concentrations through elevated medium pH. Biomass and glycerol production decreased with propanoic acid in the medium, partly contributing to increased ethanol concentration.
    Optimization of Fermentation Media for Enhancing Nitrite-oxidizing Activity by Artificial Neural Network Coupling Genetic Algorithm*
    罗剑飞, 林炜铁, 蔡小龙, 李敬源
    Chinese Journal of Chemical Engineering. 2012, 20(5):  950-957. 
    摘要 ( )   PDF (276KB) ( )  
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    Two artificial intelligence techniques, artificial neural network and genetic algorithm, were applied to optimize the fermentation medium for improving the nitrite oxidization rate of nitrite oxidizing bacteria. Experiments were conducted with the composition of medium components obtained by genetic algorithm, and the experimental data were used to build a BP (back propagation) neural network model. The concentrations of six medium components were used as input vectors, and the nitrite oxidization rate was used as output vector of the model. The BP neural network model was used as the objective function of genetic algorithm to find the optimum medium composition for the maximum nitrite oxidization rate. The maximum nitrite oxidization rate was 0.952 g NO2--N·(g MLSS)-1·d-1, obtained at the genetic algorithm optimized concentration of medium components (g·L-1): NaCl 0.58, MgSO4·7H2O 0.14, FeSO4·7H2O 0.141, KH2PO4 0.8485, NaNO2 2.52, and NaHCO3 3.613. Validation experiments suggest that the experimental results are consistent with the best result predicted by the model. A scale-up experiment shows that the nitrite degraded completely after 34 h when cultured in the optimum medium, which is 10 h less than that cultured in the initial medium.
    Nonlinear Mathematical Simulation and Analysis of Dha Regulon for Glycerol Metabolism in Klebsiella pneumoniae*
    孙亚琴, 叶剑雄, 牟晓佳, 滕虎, 冯恩民, 曾安平, 修志龙
    Chinese Journal of Chemical Engineering. 2012, 20(5):  958-970. 
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    Glycerol may be converted to 1,3-propanediol (1,3-PD) by Klebsiella pneumoniae under anaerobic conditions and glycerol dismutation involves two parallel pathways controlled by the dha regulon. In this study, a fourteen-dimensional nonlinear dynamic system is presented to describe the continuous culture and multiplicity analysis, in which two regulated negative-feedback mechanisms of repression and enzyme inhibition are investigated. The model describing the expression of gene-mRNA-enzyme-product was established according to the repression of the dha regulon by 3-hydroxypropionaldehy (3-HPA). Comparisons between simulated and experimental results indicate that the model can be used to describe the production of 1,3-PD under continuous fermentation. The new model is translated into the corresponding S-system version. The robustness of this model is discussed by using the S-system model and the sensitivity analysis shows that the model is sufficiently robust. The influences of initial glycerol concentration and dilution rate on the biosynthesis of 1,3-PD and the stability of the dha regulon model are investigated. The intracellular concentrations of glycerol, 1,3-PD, 3-HPA, repressor mRNA, repressor, mRNA and protein levels of glycerol dehydratase (GDHt) and 1,3-PD oxydoreductase (PDOR) can be predicted for continuous cultivation. The results of simulation and analysis indicate that 3-HPA accumulation will repress the expression of the dha regulon at the transcriptional level. This model gives new insights into the regulation of glycerol metabolism in K. pneumoniae and explain some of the experimental observations.
    ARX-NNPLS Model Based Optimization Strategy and Its Application in Polymer Grade Transition Process*
    费正顺, 胡斌, 叶鲁彬, 梁军
    Chinese Journal of Chemical Engineering. 2012, 20(5):  971-979. 
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    Since it is often difficult to build differential algebraic equations (DAEs) for chemical processes, a new data-based modeling approach is proposed using ARX (AutoRegressive with eXogenous inputs) combined with neural network under partial least squares framework (ARX-NNPLS), in which less specific knowledge of the process is required but the input and output data. To represent the dynamic and nonlinear behavior of the process, the ARX combined with neural network is used in the partial least squares (PLS) inner model between input and output latent variables. In the proposed dynamic optimization strategy based on the ARX-NNPLS model, neither parameterization nor iterative solving process for DAEs is needed as the ARX-NNPLS model gives a proper representation for the dynamic behavior of the process, and the computing time is greatly reduced compared to conventional control vector parameterization method. To demonstrate the ARX-NNPLS model based optimization strategy, the polyethylene grade transition in gas phase fluidized-bed reactor is taken into account. The optimization results show that the final optimal trajectory of quality index determined by the new approach moves faster to the target values and the computing time is much less.
    Reactive Distillation for Producing n-Butyl Acetate:Experiment and Simulation
    田晖, 黄智贤, 邱挺, 王晓达, 吴燕翔
    Chinese Journal of Chemical Engineering. 2012, 20(5):  980-987. 
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    In this paper, a reactive distillation (RD) column was applied for synthesis n-butyl acetate from n-butanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium stage model for separation were employed to study the RD process. The results obtained from the equilibrium stage model agreed well with the experiments. The effects of operating variables on the n-butanol conversion and n-butyl acetate purity were further investigated. The optimal column configuration for the production of n-butyl acetate was designed with 5 rectifying stages, 8 reaction stages and 13 stripping stages by the simulation study. According to the simulation results, n-butanol conversion and n-butyl acetate purity all reached greater than 96%.
    NonliNonlinear GPC with In-place Trained RLS-SVM Model for DOC Control in a Fed-batch Bioreactor*
    冯絮影, 于涛, 王建林
    Chinese Journal of Chemical Engineering. 2012, 20(5):  988-994. 
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    In this study, Saccharomyces cerevisiae (baker's yeast) was produced in a fed-batch bioreactor at the optimal dissolved oxygen concentration (DOC) and growth medium temperature. However, it is very difficult to control the DOC using conventional controllers because of the poorly understood and constantly changing dynamics of the bioprocess. A generalized predictive controller (GPC) based on a nonlinear autoregressive integrated moving average exogenous (NARIMAX) model is presented to stabilize the DOC by manipulation of air flow rate. The NARIMAX model is built by an improved recursive least-squares support vector machine, which is trained by an in-place computation scheme and avoids the computation of the inverse of a large matrix and memory reallocation. The proposed nonlinear GPC algorithm requires little preliminary knowledge of the fermentation process, and directly obtains the nonlinear model in matrix form by using iterative multiple modeling instead of linearization at each sampling period. By application of an on-line bioreactor control, experimental results demonstrate the robustness, effectiveness and advantages of the new controller.
    Isolation and Characterization of Heterotrophic Nitrifying Strain W1*
    吕永康, 王荀, 刘博凯, 刘玉香, 杨晓华
    Chinese Journal of Chemical Engineering. 2012, 20(5):  995-1002. 
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    In a high concentration substrate medium, a heterotrophic bacterium with high removal efficiency of ammonium, named W1, was isolated from activated sludge of coking wastewater treatment facility. The bacterium was Gram-negative, rod-shaped, and identified preliminarily as Alcaligenes sp. according to its morphological and physiological properties and its 16S rRNA gene sequence analysis. In the high concentration ammonium medium (400 mg·L-1 NH4--N), the effects of C source, N source, C/N ratio and initial pH of medium on ammonium removal were investigated in order to determine the optimal condition for strain W1. The maximum ammonium removal was around 95% in 4 days in an improved medium. The production of N2 gas was examined in a closed system that was full of pure oxygen at the beginning. N2 gas was detected in the system after 4 days of cultivation, which further testified that strain W1 has heterotrophic nitrification and aerobic denitrification abilities simultaneously.
    Adsorption of Chlortetracycline from Water by Rectories*
    吕国诚, 吴丽梅, 王晓龙, 廖立兵, 王小雨
    Chinese Journal of Chemical Engineering. 2012, 20(5):  1003-1007. 
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    The removal of antibiotics from water by clay minerals has become the focus of research due to their strong adsorptive ability. In this study, adsorption of chlortetracycline (CTC) onto rectories was conducted and the effects of time, concentration, temperature and pH were investigated. Experimental results showed that adsorption equilibrium was reached in 8 h. Based on the Langmuir model, the maximum adsorption capacity of CTC on rectories was 177.7 mg·g-1 at room temperature. By the study on adsorption dynamics, it is found that the kinetic date fit the pseudo-second-order model well. The adsorption of CTC by rectories is endothermic and the free energy is in the range of 10 to 30 kJ·mol-1. The pH value of solution has significant effects on adsorption and the optimal pH is at acidity (pH 2-6). At concentration of 2500 mg·L-1, the intercalated CTC produces an interlayer space with a height of 1.38 nm, which is 1.12 nm in raw rectories, suggesting that the adsorption occurs between layers of rectories.
    Effect of Moisture on Partitioning of Heavy Metals in Incineration of Municipal Solid Waste*
    蒙爱红, 李清海, 贾金岩, 张衍国
    Chinese Journal of Chemical Engineering. 2012, 20(5):  1008-1015. 
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    The effect of moisture in municipal solid waste (MSW) on partitioning of lead (Pb), zinc (Zn), copper (Cu) and cadmium (Cd) was studied in a laboratory tubular furnace by using simulated MSW. The moisture in MSW influences heavy metals in following ways, to increase the moisture in flue gas and decrease the combustion temperature, to prolong the combustion time, and to prolong the releasing time of volatiles with the furnace temperature decreased by increasing the moisture. The volatilization of Pb, Zn and Cd was enhanced by increasing the moisture in MSW because of the prolonged combustion time. For Pb and Zn, the combustion time was important at higher temperature, while for Cd, it was important at low temperature. The moisture content showed slight effect on Cu partitioning. When extra chlorine was added to MSW, such as 1%PVC+0.5%NaCl, the volatilization of Pb, Zn and Cu was enhanced by increasing the moisture because water evaporation reduced the temperature and increased devolatilization time. At higher temperature, NaCl tends to decompose and generates more free chlorine, producing more metal chlorides. Since Cd is a strong volatile heavy metal in MSW, the effect of moisture content on its volatilization is less than that of Pb, Zn or Cu during the MSW incineration.
    The Short-term Effects of Temperature and Free Ammonia on Ammonium Oxidization in Granular and Floccular Nitrifying System*
    吴蕾, 彭永臻, 马勇, 刘旭, 李凌云, 王淑莹
    Chinese Journal of Chemical Engineering. 2012, 20(5):  1016-1023. 
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    The short-term effects of temperature and free ammonia (FA) on ammonium oxidization were investigated in this study by operating several batch tests with two different partial nitrification aggregates, formed as either granules or flocs. The results showed that the rate of ammonium oxidation in both cultures increased significantly as temperature increased from 10 to 30℃. The specific ammonium oxidation rate with the granules was 2-3 times higher than that with flocs at the same temperature. Nitrification at various FA concentrations and temperatures combination exhibited obvious inhibition in ammonium oxidation rate when FA was 90 mg·L-1 and temperature dropped to 10℃ in the two systems. However, the increase in substrate oxidation rate of ammonia at 30℃ was observed. The results suggested that higher reaction temperature was helpful to reduce the toxicity of FA. Granules appeared to be more tolerant to FA attributed to the much fraction of ammonia oxidizing bacteria (AOB) and higher resistance to the transfer of ammonia into the bacterial aggregates, whereas in the floc system, the bacteria distributed throughout the entire aggregate. These results may contribute to the applicability of the nitrifying granules in wastewater treatment operated at high ammonium concentration.
    Measurements of Conductivity for Low Concentration Strong-electrolytes in Organic Solvents (Ⅰ) LiBr, LiCl, and LiNO3 in Alcohols
    陈红, 王利生, 姜波, 李弥异
    Chinese Journal of Chemical Engineering. 2012, 20(5):  1024-1033. 
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    The conductivities of LiBr, LiCl, and LiNO3 in methanol, ethanol, 1-propanol, and 2-propanol (with electrolyte concentrations <0.08 mol·L-1) were determined at 298.15 K, 313.15 K, and 323.15 K at atmosphere pressure separately by using a conductivity meter. The conductivity data were correlated with Foss-Chen-Justice (FCJ) equation and the limiting molar conductivities were obtained. The mean ionic activity coefficients of the salts in the organic solvents were calculated according to the Debye-Hückel limiting law and Onsager-Falkenhangen equations. The calculated results were compared with those activity coefficients in literature.
    Effect of Polyethylene Glycol on the Properties of γ-Al2O3 Formation by Polyaluminum Chloride*
    赵长伟, 王孝年, 何劲松, 王园园, 栾兆坤
    Chinese Journal of Chemical Engineering. 2012, 20(5):  1034-1038. 
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    A polyaluminium chloride solution with high Al13 content self-prepared was used as material for preparing the spherical γ-Al2O3 by the sol-gel and oil-drop method. Polyethylene glycol with different molecular mass was used as surfactant to investigate the effect on property of γ-Al2O3. The physical property was characterized by 27Al NMR (nuclear magnetic resonance) spectra, X-ray diffraction, FT-IR (Fourier transform infrared spectroscopy) and TG-DTA (thermogravimetric-differential thermal analysis). The results showed that surface area, pore volume and pore size of γ-Al2O3 all increased with the increase of polyethylene glycol molecular mass in the experimental research range, and polyethylene glycol 10000 was the most suitable pore forming additive. γ-Al2O3 with surface area of 339 m2·g-1, pore volume of 0.59 cm3·g-1 and pore diameter of 6.9 nm were obtained at 450℃.