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SCI和EI收录∣中国化工学会会刊
本期目录
2014年 第22卷 第11/12期 刊出日期:2014-12-28
    流体力学与传递现象
    Numerical Simulation of Liquid-Solid Countercurrent Fluidization inside an Extraction Column Based on Particle Trajectory Model
    Zhongyuan Li, Xingang Li, Hong Sui, Hong Li
    . 2014, 22(11/12):  1179-1186.  doi:10.1016/j.cjche.2014.09.019
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    The liquid-solid countercurrent fluidization process in an extraction columnwas numerically simulated based on the particle trajectorymodel of Eulerian-Lagrangianmethod. The simulation approach was validated by previous experiments. A power function correlationwas proposed for dimensionless slip velocity Uslip/Ut and hold-up fraction ϕ, and the operational zone in the countercurrent fluidizationwas determined. Simultaneous countercurrent fluidization of particles with different diameters was also simulated. The comparison shows that the simulation results are consistentwith the calculation values fromthemulti-particle free sedimentation model based on noninterference assumption, verifying the reliability of the approach in present work.
    分离科学与工程
    Removal of Aniline from Wastewater Using Hollow Fiber Renewal Liquid Membrane
    Zhongqi Ren, Xinyan Zhu, Wei Liu, Wei Sun, Weidong Zhang, Junteng Liu
    . 2014, 22(11/12):  1187-1192.  doi:10.1016/j.cjche.2014.09.035
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    Hollow fiber renewal liquidmembrane (HFRLM)methodwas proposed based on the surface renewal theory for removal of aniline from waste water. The system of aniline + D2EHPA in kerosene + HCl was used. Aqueous layer diffusion in the feed phase is the rate-control step, and the influence of lumen side flow rate on the mass transfer is more significant than that on the shell side. The resistance of overall mass transfer is greatly reduced because of the mass transfer intensification in the renewal of liquid membrane on the lumen side. The driving force of mass transfer can be considered as a function of distribution equilibrium, and the overall mass transfer coefficient increases with the increase of pH in the feed solution, HCl concentration and D2EHPA concentration, and decreases with the increase of initial aniline concentration. A mass transfermodel is developed forHFRLMbased on the surface renewal theory. The calculated results agree well with experimental results. The HFRLM process is a promising method for aniline wastewater treatment.
    Kinetics, Isotherms and Equilibrium Study of Co(II) Adsorption from Single and Binary Aqueous Solutions by Acacia nilotica Leaf Carbon
    P. Thilagavathy, T. Santhi
    . 2014, 22(11/12):  1193-1198.  doi:10.1016/j.cjche.2014.08.006
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    The removal of cobalt ion from aqueous solution by Acacia nilotica leaf carbon (HAN), is described. Effect of pH, agitation time and initial concentration on adsorption capacities of HAN was investigated in a batch mode. The adsorption process, which is pH dependent, shows maximum removal of cobalt in the pH range 5 for an initial cobalt concentration of 50mg·L-1 The experimental data have been analyzed by using the Freundlich, Langmuir, Temkin and Dubinin-Radushkevich isotherm models. The batch sorption kinetics have been tested for a pseudofirst order, pseudo-second order and Elovich kinetic models. The rate constants of adsorption for all these kinetic models have been calculated. Results showed that the intraparticle diffusion and initial sorption of Co(II) into HAN was themain rate limiting step. The adsorption of cobalt ion was confirmed through instrumental analyses such as scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FTIR). The desorption and recycling ability of HAN were also found. We conclude that HAN can be used for the efficient removal of cobalt from aqueous solution.
    催化、动力学与反应工程
    One-step Continuous Phenol Synthesis Technology via Selective Hydroxylation of Benzene over Ultrafine TS-1 in a Submerged Ceramic Membrane Reactor
    Hong Jiang, Fei She, Yan Du, Rizhi Chen, Weihong Xing
    . 2014, 22(11/12):  1199-1207.  doi:10.1016/j.cjche.2014.09.016
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    A newroute towards phenol production by one-step selective hydroxylation of benzenewith hydrogen peroxide over ultrafine titaniumsilicalites-1 (TS-1) in a submerged ceramic membrane reactorwas developed, which can maintain the in situ removal of ultrafine catalyst particles fromthe reaction slurry and keep the process continuous. The effects of key operating parameters on the benzene conversion and phenol selectivity, as well as themembrane filtration resistance were examined by single factor experiments. A continuous reaction process was carried out under the obtained optimumoperation conditions. Results showed that the systemcan be continuously and stably operated over 20 h, and the benzene conversion and phenol selectivity kept at about 4% and 91%, respectively. The ceramic membrane exhibits excellent thermal and chemical stability in the continuous reaction process.
    Effect of Gasifying Medium on the Coal Chemical Looping Gasification with CaSO4 as Oxygen Carrier
    Yongzhuo Liu, Weihua Jia, Qingjie Guo, Hojung Ryu
    . 2014, 22(11/12):  1208-1214.  doi:10.1016/j.cjche.2014.09.011
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    The chemical looping gasification uses an oxygen carrier for solid fuel gasification by supplying insufficient lattice oxygen. The effect of gasifyingmedium on the coal chemical looping gasification with CaSO4 as oxygen carrier is investigated in this paper. The thermodynamical analysis indicates that the addition of steam and CO2 into the system can reduce the reaction temperature, at which the concentration of syngas reaches its maximum value. Experimental result in thermogravimetric analyzer and a fixed-bed reactor shows that the mixture sample goes through three stages, drying stage, pyrolysis stage and chemical looping gasification stage, with the temperature for three different gaseousmedia. The peak fitting and isoconversional methods are used to determine the reaction mechanism of the complex reactions in the chemical looping gasification process. It demonstrates that the gasifying medium (steam or CO2) boosts the chemical looping process by reducing the activation energy in the overall reaction and gasification reactions of coal char. However, themechanism using steamas the gasifying medium differs from that using CO2.With steam as the gasifying medium, parallel reactions occur in the beginning stage, followed by a limiting stage shifting from a kinetic to a diffusion regime. It is opposite to the reaction mechanism with CO2 as the gasifying medium.
    Lipase Catalyzed Synthesis of Medium-chain Biodiesel from Cinnamonum camphora Seed Oil
    Junfeng Liu, Li Deng, Meng Wang, Kaili Nie, Luo Liu, Tianwei Tan, Fang Wang
    . 2014, 22(11/12):  1215-1219.  doi:10.1016/j.cjche.2014.09.011
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    The non-edible camphor tree seed oil was extracted and catalyzed by immobilized lipase for biodiesel production. The oil yield from camphor tree seeds reached 35.2% of seed weight by twice microwave-assisted extractions. Gas chromatography showed that free fatty acid content in camphor tree seed oil was 1.88%, and the main fatty acids were capric acid (53.4%) and lauric acid (38.7%).With immobilized lipase Candida sp. 99-125 as catalyst, several important factors for reaction conditions were examined through orthogonal experiments. The optimum conditions were obtained: water content and enzyme loading were both 15% with a molar ratio of 1:3.5 (oil/ethanol), and the process of alcoholysis was in nine steps at 40 ℃ for 24 h, with agitation at 170 r·min-1. As a result, the medium-chain biodiesel yield was 93.5%. The immobilized lipase was stable when it was used repeatedly for 210 h.
    Hydroxylation of Benzene to Phenol by H2O2 over an Inorganic-Organic Dual Modified Heteropolyacid
    Li Jing, Fumin Zhang, Yijun Zhong, Weidong Zhu
    . 2014, 22(11/12):  1220-1225.  doi:10.1016/j.cjche.2014.09.041
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    Various catalysts, including the heteropolyacid (HPA) H4PMo11VO40, its cesiumsalts, and inorganic-organic dual modified HPA catalyst,were prepared and characterized by Fourier transform infrared spectroscopy (FT-IR), nuclearmagnetic resonance (13C NMR), N2 adsorption, acid-base titration, electron spin resonance (ESR) and X-ray diffraction (XRD) techniques as well as elemental analysis. These prepared catalysts were used in the hydroxylation of benzene to phenol by H2O2 as oxidant. The inorganic-organic dual modified HPA Cs2.5(MIMPS)1.5 PMo11VO40, prepared by partially exchanging Cs+ with protons in H4PMo11VO40 and followed by the immobilization of 3-(1-methylimidazolium-3-yl)propane-1-sulfonate (MIMPS), led to a liquid-solid biphasic catalysis system in the hydroxylation, which showed the best catalytic performance in terms of reusability and catalytic activity. The high reusability of Cs2.5(MIMPS)1.5PMo11VO40 in the heterogeneous hydroxylation was probably due to its high resistance in leaching of bulk HPA into the reaction medium. The slightly enhanced catalytic activity for the catalyst was due to the acid sites available from MIMPS beneficial to the hydroxylation.
    Effect of Al Content on the Isomerization Performance of Solid Superacid Pd-S2O82-/ZrO2-Al2O3
    Hua Song, Na Wang, Hualin Song, Feng Li, Zaishun Jin
    . 2014, 22(11/12):  1226-1231.  doi:10.1016/j.cjche.2014.07.002
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    The effect of Al content on the performance of the Pd-S2O82-/ZrO2-Al2O3 solid superacid catalystwas studied using n-pentane isomerization as a probe reaction. The catalysts were also characterized by X-ray diffraction (XRD), Fourier transform Infrared (FTIR), specific surface area measurements (BET), thermogravimetry-differential thermal analysis (TG-DTA), H2-temperature programmed reduction (TPR) and NH3 temperature-programmed desorption (NH3-TPD). The Pd-S2O82-/ZrO2-Al2O3 catalyst made from Al2O3 mass fraction of 2.5% exhibited the best performance and its catalytic activity increased by 44.0% compared with Pd-S2O82-/ZrO2. The isopentane yield reached 64.3% at a temperature of 238℃, a reaction pressure of 2.0 MPa, a space velocity of 1.0 h-1 and a H2/n-pentane molar ratio of 4.0. No obvious catalyst deactivation was observed within 100 h.
    Dehydrogenation of Propane on Pt or PtSn Catalysts with Al2O3 or SBA-15 Support
    Jing Feng, Mingsen Zhang, Yuanyi Yang
    . 2014, 22(11/12):  1232-1236.  doi:10.1016/j.cjche.2013.07.001
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    Dehydrogenation of propane on Pt or PtSn catalyst over Al2O3 or SBA-15 support was investigated. The catalysts were characterized by CO-pulse chemisorption, thermogravimetry, temperature-programmed-reduction of H2, and diffuse reflectance infrared Fourier transform spectroscopy of absorbed CO. The results show that the platinum species is in oxidation state in the catalyst on Al2O3 support, so the catalyst must be reduced in H2 before dehydrogenation reaction. Addition of Sn improves the Pt dispersion, but the catalyst deactivates rapidly because of the coke formation. The interaction of Pt and Al2O3 is strong. On SBA-15 support, the platinum species is completely reduced to Pt0 in the calcination process, so the reduction is not needed. Addition of Sn improves the activity and selectivity of the catalyst. The interaction of Pt and SBA-15 is weak, so it is easy for Pt particles to sinter.
    In Situ Delamination of Ferrierite Zeolite and its Performance in the Catalytic Cracking of C4 Hydrocarbons
    Ruili Pan, Miaojuan Jia, Yuping Li, Xiaofeng Li, Tao Dou
    . 2014, 22(11/12):  1237-1242.  doi:10.1016/j.cjche.2014.09.006
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    Ferrierite (FER) zeolites were synthesized by solid transformation at different alkalinities (OH-/Al2O3 molar ratios). The in situ delamination of FER zeolites were achieved and their catalytic performances in the catalytic cracking of C4 hydrocarbons were examined. The relationships among the OH-/Al2O3 molar ratio, FER structure, composition, surface acidity and catalytic performance in C4 hydrocarbon crackingwere investigated. The results of X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electronmicroscopy, inductively coupled plasma atomic emission spectroscopy, N2 adsorption, NH3 temperature-programmed desorption and catalytic cracking showed that with increasing OH-/Al2O3 molar ratio in the synthesis gel, the SiO2/Al2O3 molar ratio of the as-synthesized FER zeolite decreased, the amount of acid sites in the corresponding H-FER increased, and the acid strengthweakened. Additionally, the FER zeolitewas delaminated at themesoscale. H-FER5 synthesized at the highest alkalinity had the largest number of acid sites and exhibited the highest catalytic activity in C4 hydrocarbon catalytic cracking among three of the prepared catalysts. H-FER3 synthesized at the secondhighest alkalinity showed that the highest yield of benzene and toluene because of the secondary pores resulted from the gaps between the layers, which were beneficial to the diffusion and formation of large molecules.
    过程系统工程与过程安全
    A Kernel Time Structure Independent Component Analysis Method for Nonlinear Process Monitoring
    Lianfang Cai, Xuemin Tian, Ni Zhang
    . 2014, 22(11/12):  1243-1253.  doi:10.1016/j.cjche.2014.09.021
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    Kernel independent component analysis (KICA) is a newly emerging nonlinear process monitoring method, which can extractmutually independent latent variables called independent components (ICs) fromprocess variables. However, when more than one IC have Gaussian distribution, it cannot extract the IC feature effectively and thus its monitoring performance will be degraded drastically. To solve such a problem, a kernel time structure independent component analysis (KTSICA) method is proposed for monitoring nonlinear process in this paper. The original process data are mapped into a feature space nonlinearly and then the whitened data are calculated in the feature space by the kernel trick. Subsequently, a time structure independent component analysis algorithm, which has no requirement for the distribution of ICs, is proposed to extract the IC feature. Finally, two monitoring statistics are built to detect process faults. When some fault is detected, a nonlinear fault identification method is developed to identify fault variables based on sensitivity analysis. The proposed monitoring method is applied in the Tennessee Eastman benchmark process. Applications demonstrate the superiority of KTSICA over KICA.
    Soft Computing of Biochemical Oxygen Demand Using an Improved T-S Fuzzy Neural Network
    Junfei Qiao, Wei Li, Honggui Han
    . 2014, 22(11/12):  1254-1259.  doi:10.1016/j.cjche.2014.09.023
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    It is difficult to measure the online values of biochemical oxygen demand (BOD) due to the characteristics of nonlinear dynamics, large lag and uncertainty in wastewater treatment process. In this paper, based on the knowledge representation ability and learning capability, an improved T-S fuzzy neural network (TSFNN) is introduced to predict BOD values by the soft computing method. In this improved TSFNN, a K-means clustering is used to initialize the structure of TSFNN, including the number of fuzzy rules and parameters of membership function. For training TSFNN, a gradient descent method with the momentum item is used to adjust antecedent parameters and consequent parameters. This improved TSFNN is applied to predict the BOD values in effluent of the wastewater treatment process. The simulation results show that the TSFNN with K-means clustering algorithm can measure the BOD values accurately. The algorithm presents better approximation performance than some other methods.
    Multimode Process Fault Detection Using Local Neighborhood Similarity Analysis
    Xiaogang Deng, Xuemin Tian
    . 2014, 22(11/12):  1260-1267.  doi:10.1016/j.cjche.2014.09.022
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    Traditional data driven fault detection methods assume unimodal distribution of process data so that they often perform not well in chemical process withmultiple operating modes. In order tomonitor themultimode chemical process effectively, this paper presents a novel fault detection method based on local neighborhood similarity analysis (LNSA). In the proposed method, prior process knowledge is not required and only themultimode normal operation data are used to construct a reference dataset. For online monitoring of process state, LNSA applies moving window technique to obtain a current snapshot data window. Then neighborhood searching technique is used to acquire the corresponding local neighborhood data window from the reference dataset. Similarity analysis between snapshot and neighborhood data windows is performed, which includes the calculation of principal component analysis (PCA) similarity factor and distance similarity factor. The PCA similarity factor is to capture the change of data direction while the distance similarity factor is used for monitoring the shift of data center position. Based on these similarity factors, two monitoring statistics are built for multimode process fault detection. Finally a simulated continuous stirred tank systemis used to demonstrate the effectiveness of the proposed method. The simulation results showthat LNSA can detect multimode process changes effectively and performs better than traditional fault detection methods.
    Recursive State-space Model Identification of Non-uniformly Sampled Systems Using Singular Value Decomposition
    Hongwei Wang, Tao Liu
    . 2014, 22(11/12):  1268-1273.  doi:10.1016/j.cjche.2014.09.028
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    In this paper a recursive state-space model identification method is proposed for non-uniformly sampled systems in industrial applications. Two cases for measuring all states and only output(s) of such a system are considered for identification. In the case of statemeasurement, an identification algorithm based on the singular value decomposition (SVD) is developed to estimate the model parameter matrices by using the least-squares fitting. In the case of output measurement only, another identification algorithm is given by combining the SVD approach with a hierarchical identification strategy. An example is used to demonstrate the effectiveness of the proposed identification method.
    A Novel Empirical Equation for Relative Permeability in Low Permeability Reservoirs
    Yulei Ge, Shurong Li, Kexin Qu
    . 2014, 22(11/12):  1274-1278.  doi:10.1016/j.cjche.2014.09.031
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    In this paper, a novel empirical equation is proposed to calculate the relative permeability of low permeability reservoir. An improved itemis introduced on the basis of Rose empirical formula and Al-Fattah empirical formula, with one simple model to describe oil/water relative permeability. The position displacement idea of bare bones particle swarm optimization is applied to change themutation operator to improve the RNA genetic algorithm. The parameters of the new empirical equation are optimizedwith the hybrid RNA genetic algorithm (HRGA) based on the experimental data. The data is obtained from a typical low permeability reservoir well 54 core 27-1 in GuDong by unsteady method.We carry out matlab programming simulation with HRGA. The comparison and error analysis show that the empirical equation proposed is more accurate than the Rose empirical formula and the exponential model. The generalization of the empirical equation is also verified.
    Energy Efficiency Evaluation Based on Data Envelopment Analysis Integrated Analytic Hierarchy Process in Ethylene Production
    Yongming Han, Zhiqiang Geng, Qiyu Liu
    . 2014, 22(11/12):  1279-1284.  doi:10.1016/j.cjche.2014.09.032
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    Energy efficiency data from ethylene production equipment are of high dimension, dynamic and time sequential, so their evaluation is affected bymany factors.Abnormal data from ethylene production are eliminated through consistency test,making the data consumption uniformto improve the comparability of data.Due to the limit of input and output data of decision making unit in data envelopment analysis (DEA), the energy efficiencydata fromthe same technology in a certain year are disposed monthly using DEA. The DEA data of energy efficiency from the same technology are weighted and fused using analytic hierarchy process. The energy efficiency data from different technologies are evaluated by their relative effectiveness to find the direction of energy saving and consumption reduction.
    化工热力学
    Adsorption Behavior of Rhodamine B on UiO-66
    Qinqin He, Qi Chen, Mengmeng Lü, Xueting Liu
    . 2014, 22(11/12):  1285-1290.  doi:10.1016/j.cjche.2014.09.009
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    The adsorption characteristics of UiO-66 (a Zr-containing metal-organic framework formed by terephthalate) for Rhodamine B (RhB), such as isotherms, kinetics and thermodynamics, were investigated systematically. The batch adsorption data conform well to the Langmuir and Freundlich isotherms. The adsorption kinetics of UiO-66 for RhB can be well described by the pseudo first-order model, and the adsorption thermodynamic parametersΔG0, ΔH0 and ΔS0 at 273 K are-6.282 kJ·mol-1, 15.096 kJ·mol-1 and 78.052 J·mol-1·K-1, respectively. The thermodynamic analyses show that the adsorption process of RhB on UiO-66 is more favorable at higher temperatures. UiO-66 can be regenerated by desorbing in DMF solution with ultrasonic for 1 h. UiO-66 can keep good performance for at least six cycles of sorption/desorption.
    Crossover Equation of State for Selected Hydrocarbons (C4-C7)
    Aijing Shen, Qiang Liu, Yuanyuan Duan, Zhen Yang
    . 2014, 22(11/12):  1291-1297.  doi:10.1016/j.cjche.2014.09.013
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    The organic Rankine cycle (ORC) has attracted attention for waste heat recovery and renewable energy systems. An accurate prediction for thermodynamic properties of working fluids is of great importance for cycle performance evaluations and system design. Particularly, hydrocarbons are promising for their good performance and low global warming potentials. Moreover, the thermal efficiency of the ORC is higher when the evaporation temperature is closer to the critical temperature, which makes the properties in the critical region rather important. Recent research has shown that using mixture as working fluid can achieve better temperature matches. Therefore, an equation of state (EoS) that can be extended to mixture calculations is more attractive. Specific EoS for selected hydrocarbons is precise, but very complex. Cubic EoSs, such as widely used Peng-Robinson EoS and Soave-Redlich-Kwong (SRK) EoS, fail to accurately predict liquid densities over wide pressure ranges or pressure-density-temperature (pρT) properties in the near-critical region. This work combines the volume translation approach and the crossover method to provide better prediction for thermodynamic properties in the critical region and in regions far from the critical point. A crossover volume translation SRK EoS is developed and used for n-butane, i-butane, n-pentane, i-pentane, n-hexane, i-hexane and n-heptane. The volume translation term is set as a constant to ensure the accuracy of the saturated liquid density at low reduced temperatures. Then, the crossover method is introduced into the volume translation EoS to improve the predictions of thermodynamic properties in the critical region. Six crossover parameters are used, which are constants or functions of acentric factor and critical parameters. Therefore, none of the parameters in the crossover volume translation SRK EoS is adjustable, which makes the crossover EoS totally predictive and easily extend tomixtures. Comparisons show that the crossover EoS is in much better agreement with experimental data than the original SRK EoS.
    Liquid-Liquid Equilibria of Ternary Systems cis-1,2-Dimethylcyclohexane + Toluene + Sulfolane
    Xiaoyan Sun, Shuguang Xiang
    . 2014, 22(11/12):  1298-1301.  doi:10.1016/j.cjche.2013.05.003
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    Liquid-Liquid Equilibrium (LLE) data for three Ternary Systems comprising cis-1,2-dimethylcyclohexane + toluene + sulfolane were measured at 298.15, 313.15 and 328.15 K under atmospheric pressure. The phase diagrams for the ternary systems were presented. The reliability of the experiment data was tested using the Othmer-Tobias correlation. The LLE data were then correlated with the universal functional activity coefficient for liquid-liquid systems (UNIF-LL) and non-random two liquid using dataset 2 (NRTL/2) activity coefficient models to obtain the binary interaction parameters as programmed by the Aspen Plus simulation. The results showed that the experimental data were satisfactorily represented by both the UNIF-LL and the NRTL/2 models as revealed from the very small values of the root mean square error and the absolute deviation in composition.
    Interfacial Tension of CO2 and Organic Liquid under High Pressure and Temperature
    Zihao Yang, Mingyuan Li, Bo Peng, Meiqin Lin, Zhaoxia Dong, Yong Ling
    . 2014, 22(11/12):  1302-1306.  doi:10.1016/j.cjche.2014.09.042
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    In order to investigate the effect of organic liquidmolecular structure and the intermolecular force operatingwith CO2 molecules and organic liquid molecules on interfacial tension (IFT) between CO2 and organic liquid at the first contact, the interfacial tension between CO2 and hexane, octane, ethanol and cyclohexane at different temperatures and pressures ismeasured by using the pendant drop method and the axisymmetric drop shape analysis (ADSA). The results show that the interfacial tension between CO2 and organic liquids is affected by the polarity and the structure of the organic liquid molecule obviously. The intermolecular force operating within CO2 molecules or organic liquid, and that between CO2 and organic liquids molecules play a dominate role on the interfacial tension between CO2 and the organic liquids.
    A Molecular Thermodynamic Model for Restricted Swelling Behaviors of Thermo-sensitive Hydrogel
    Cheng Lian, Dongyan Zhi, Shouhong Xu, Honglai Liu
    . 2014, 22(11/12):  1307-1313.  doi:10.1016/j.cjche.2014.08.004
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    A molecular thermodynamic model was developed for describing the restricted swelling behavior of a thermosensitive hydrogel confined in a limited space. The Gibbs free energy includes two contributions, the contribution of mixing of polymer and solvent calculated by using the lattice model of randompolymer solution, and the contribution due to the elasticity of polymer network. This model can accurately describe the swelling behavior of restricted hydrogels under uniaxial and biaxial constraints by using twomodel parameters. One is the interaction energy parameter between polymer network and solvent, and the other is the size parameter depending on the degree of cross-linking. The calculated results show that the swelling ratio reduces significantly and the phase transition temperature decreases slightly as the restricted degree increases, which agree well with the experimental data.
    生物技术与生物工程
    Enhancement of Lipase-catalyzed Synthesis of Caffeic Acid Phenethyl Ester in Ionic Liquid with DMSO Co-solvent
    Shuangshuang Gu, Jun Wang, Xianbin Wei, Hongsheng Cui, Xiangyang Wu, Fuan Wu
    . 2014, 22(11/12):  1314-1321.  doi:10.1016/j.cjche.2014.09.024
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    Caffeic acid phenethyl ester (CAPE) is a natural and rare ingredientwith several biological activities, but its industrial production using lipase-catalyzed esterification of caffeic acid (CA) and 2-phenylethanol (PE) in ionic liquids (ILs) is hindered by low substrate concentrations and long reaction time. To set up a high-efficiency bioprocess for production of CAPE, a novel dimethyl sulfoxide (DMSO)-IL co-solvent system was established in this study. The 2% (by volume) DMSO-[Bmim][Tf2N] system was found to be the best medium with higher substrate solubility and conversion of CA. Under the optimum conditions, the substrate concentration of CA was raised 8-fold, the reaction timewas reduced by half, and the conversion reached 96.23%. The kinetics follows a ping-pong bi-bi mechanismwith inhibition by PE, with kinetic parameters as follows: Vmax=0.89mmol · min-1·g-1, Km,CA= 42.9mmol·L-1, Km,PE= 165.7mmol·L-1, and Ki,PE= 146.2mmol·L-1. The results suggest that the DMSO cosolvent effect has great potential to enhance the enzymatic synthesis efficiency of CAPE in ILs.
    Enhancing the Activity of Glutamate Decarboxylase from Lactobacillus brevis by Directed Evolution
    Ling Lin, Sheng Hu, Kai Yu, Jun Huang, Shanjing Yao, Yinlin Lei, Guixiang Hu, Lehe Mei
    . 2014, 22(11/12):  1322-1327.  doi:10.1016/j.cjche.2014.09.025
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    Glutamate decarboxylase (GAD, EC4.1.1.15) can catalyze the decarboxylation of L-glutamate to form γ- aminobutyrate (GABA), which is in great demand in some foods and pharmaceuticals. In our previous study, gad, the gene coding glutamate decarboxylase from Lactobacillus brevis CGMCC 1306, was cloned and its soluble expression was realized. In this study, error-prone PCR was conducted to improve its activity, followed by a screening. Mutant Q51H with high activity [55.4 mmol·L-1·min-1·(mg protein)-1, 120% higher than that of the wild type at pH 4.8] was screened out from the mutant library. In order to investigate the potential role of this site in the regulation of enzymatic activity, site-directed saturation mutagenesis at site 51 was carried out, and three specific mutants, N-terminal truncated GAD, Q51P, and Q51L, were identified. The kinetic parameters of the three mutants and Q51Hwere characterized. The results reveal that aspartic acid at site 88 and N-terminal domain are essential to the activity aswell as correct folding of GAD. This study not only improves the activity of GAD, but also sheds new light on the structure-function relationship of GAD.
    Enzyme-catalyzed Sequential Reduction of Carbon Dioxide to Formaldehyde
    Wenfang Liu, Yanhui Hou, Benxiang Hou, Zhiping Zhao
    . 2014, 22(11/12):  1328-1332.  doi:10.1016/j.cjche.2014.09.026
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    It has been reported that enzymatic-catalyzed reduction of CO2 is feasible.Most of literature focuses on the conversion of CO2 to methanol.Hereinwe put emphasis on the sequential conversion of CO2 to formaldehyde and its single reactions. It appears that CO2 pressure plays a critical role and higher pressure is greatly helpful to form more HCOOH as well as HCHO. The reverse reaction became severe in the reduction of CO2 to formaldehyde after 10 h, decreasing HCHO production. Increasing the mass ratio of formate dehydrogenase to formaldehyde dehydrogenase could promote the sequential reaction. At concentrations of nicotinamide adenine dinucleotide lower than 100 mmol·L-1, the reduction of CO2 was accelerated by increasing cofactor concentration. The optimum pH value and concentration of phosphate buffer were determined as 6.0 and 0.05 mol·L-1, respectively, for the overall reaction. It seems that thermodynamic factor such as pH is restrictive to the sequential reaction due to distinct divergence in appropriate pH range between its single reactions.
    Lipase Immobilization onto the Surface of PGMA-b-PDMAEMA-grafted Magnetic Nanoparticles Prepared via Atom Transfer Radical Polymerization
    Jingyun Wang, Fangling Ji, Jishuang Xing, Shuang Cui, Yongming Bao, Wenbo Hao
    . 2014, 22(11/12):  1333-1339.  doi:10.1016/j.cjche.2014.09.029
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    A block copolymer of 2-dimethylaminoethyl methacrylate (DMAEMA) and glycidyl methacrylate (GMA) was grafted onto the surface of magnetic nanoparticles (Fe3O4) via atom transfer radical polymerization. The resultant PGMA-b-PDMAEMA-grafted-Fe3O4 magnetic nanoparticles with amino and epoxy groups were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, thermo-gravimetric analysis, and scanning electron microscopy. Lipase from Burkholderia cepacia was successfully immobilized onto the magnetic nanoparticles by physical adsorption and covalent bonding. The immobilization capacity of the magnetic particles is 0.5 mg lipase per mg support, with an activity recovery of up to 43.1% under the optimum immobilization condition. Biochemical characterization shows that the immobilized lipase exhibits improved thermal stability, good tolerance to organic solvents with high lg P, and higher pH stability than the free lipase at pH 9.0. After six consecutive cycles, the residual activity of the immobilized lipase is still over 55% of its initial activity.
    能源、资源与环境技术
    Exploration of As(III)/As(V) Uptake from Aqueous Solution by Synthesized Calcium Sulfate Whisker
    Xiaojuan Chen, Liuchun Yang, Junfeng Zhang, Yan Huang
    . 2014, 22(11/12):  1340-1346.  doi:10.1016/j.cjche.2014.09.018
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    Although common calcium-containing minerals such as calcite and gypsum may fix arsenic, the interaction betweenmodified calcic minerals and arsenic has seldombeen reported. The uptake behavior of As(III)/As(V) from aqueous solutions by calcium sulfate whisker (CSW, dihydrate or anhydrite) synthesized through a cooling recrystallization method was explored. A series of batch experiments were conducted to examine the effect of pH, reaction time, whisker dosage, and initial As concentration. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize the samples prepared. The results showed that pH of the aqueous solution was an important parameter for As(III)/As(V) uptake, and an excellent removal efficiency could be achieved under strongly alkaline condition. The data from batch experiments for reaction of As(V) with calcium sulfate dihydrate whisker (CSDW) and calcium sulfate anhydrous whisker (CSAW) were well described with extended Langmuir EXT1 model, from which theoretic maximum adsorption capacity of 46.57 mg As(V)·(g CSDW)-1 and 39.18 mg As(V)·(g CSAW)-1 were obtained. Some calcium arsenate solids products, such as CaAsO3(OH) (weilite, syn), Ca3(AsO4)2 (calcium arsenate), CaO-As2O5, Ca-As-O, Ca5(AsO4)3OH·xH2O (calcium arsenate hydroxide hydrate), and CaH(AsO4)·2H2O (hydrogen calcium arsenic oxide hydrate), were detected at pH = 12.5 through XRD analysis. This indicates that the interaction mechanism between As(V) and CSWis a complex adsorption process combined with surface dissolution and chemical precipitation.
    Effects of Sorbents on the Partitioning and Speciation of Cu During Municipal Solid Waste Incineration
    Hui Zhou, Jin Sun, Aihong Meng, Qinghai Li, Yanguo Zhang
    . 2014, 22(11/12):  1347-1351.  doi:10.1016/j.cjche.2014.09.030
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    Oxides of silicon, aluminium and calcium are normally dominant minerals during municipal solid waste (MSW) combustion. In flue gas, SiO2, Al2O3 and CaO all act as sorbents capturing heavy metals (and semi-volatile organics). To further understand the effect of sorbents during MSW combustion, the effects of SiO2, Al2O3 and CaO on Cu partitioning were experimentally investigated by the combustion of synthetic MSW in a tubular furnace and their effects on Cu speciation were studied by thermodynamic equilibrium calculations using ChemKin software. The experiments show that CaO has the highest Cu sorption efficiency at 900 ℃, followed by Al2O3 and SiO2. Thermodynamic equilibrium calculations show that for Cu the addition of SiO2 and Al2O3 reduces the amount of liquid CuCl, which is more volatile. However, the addition of CaO has little influence on chemical sorption of Cu, indicating that the sorption of CaO is resulted from physical sorption.
    材料与产品工程
    Preparation of Silica-Alumina Hollow Spheres with a Single Surface Hole by Co-axial Microchannel
    Jinyuan Wang, Yujun Wang, Guangsheng Luo
    . 2014, 22(11/12):  1352-1356.  doi:10.1016/j.cjche.2014.09.017
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    Si/Al composite hollow spheres with a surface hole were prepared with the co-axial microchannel in a one-step method. It is easy to use the technique for size control and continuous operation. At Si/Al ratio between 4 and 5, a hole forms on the surface, due to the fast gelation process and high viscosity of the sol. Scanning electron microscopy, nitrogen adsorption-desorption isotherms, and mercury intrusion method are used to characterize the samples. The hole size is 40-150 μm and the particle size is 450-600 μm. The size can be adjusted by the flow rate of the oil phase.
    Preparation and Characterization of Biological Non-toxic Hybrid Nanoparticles Based on Lactide and Poly(ethylene glycol) Loading Docetaxel for Anticancer Drug Delivery
    Ruiduan Li, Jianjun Zhang, Jianfeng Chen, Wei Teng, Jiexin Wang, Caixia Li
    . 2014, 22(11/12):  1357-1362.  doi:10.1016/j.cjche.2014.09.012
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    Hybrid nanoparticles based on lactide and poly(ethylene glycol) were composed of a copolymer, poly(2- amino,1,3-propanediol carbonic ester-co-lactide) [P(LA-co-CA)], and a graft copolymer, poly(2-amino,1,3- propanediol carbonic ester-co-L-lactide)-g-methoxy-poly(ethylene glycol) [P(LA-co-CA)-mPEG]. The hybrid nanoparticles were prepared using emulsion solvent diffusion method. The copolymer of poly(2-benzyloxy amide,1,3-propanediol carbonic ester-co-lactide) was prepared using ring-opening polymerization with diethylzinc (ZnEt2) as a catalyst, and then took off benzyl oxygen group to obtain P(LA-co-CA). P(LA-co-CA)-mPEG by grafting methoxy-PEG-propionaldehyde (mPEG-ALD) on P(LA-co-CA). With docetaxel as a model drug, the morphology of nanoparticles was characterized by scanning electron microscopy (SEM) and the size and size distributionwere determined by dynamic light scattering (DLS). The size of DTX-loaded particle was approximately 110 nm. The size scale prevents themfrom uptake by the reticulo-endothelial system and accumulation at the target site through the enhanced permeability and retention effect. InMTT assay, the results showed that the polymers are non-cytotoxic. The study points to the potential application of the composite nanoparticles in biomedical applications, including tissue engineering and controlled drug delivery.
    Effect of Temperature on Phase and Alumina Extraction Efficiency of the Product from Sintering Coal Fly Ash with Ammonium Sulfate
    Yusheng Wu, Ping Xu, Jiao Chen, Laishi Li, Mingchun Li
    . 2014, 22(11/12):  1363-1367.  doi:10.1016/j.cjche.2014.09.008
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    A new developed technology for extracting alumina from coal fly ash was studied in this paper. In this technology, coal fly ash is first sintered with ammonium sulfate, forming ammonium aluminum sulfate in the resultant product, where alumina can be easily leached without using any strong acid or alkali. The products obtained under different sintering conditions were characterized by X-ray diffractometry. Alumina extraction efficiency of these products was also investigated. The results show that the sintering temperature and time substantially influence the phase composition and alumina extraction efficiency of sintered products, while the heating rate has little influence. The optimal sintering condition is 400 ℃ for 3 h in air with a heating rate of 6 ℃·min-1. Under the optimal sintering condition, the alumina extraction efficiency from as-sintered coal fly ash can reach 85% or more.