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SCI和EI收录∣中国化工学会会刊
本期目录
2009年 第17卷 第3期 刊出日期:2009-06-28
    Proposed Models for Subcritical Water Extraction of Essential Oils
    M. Khajenoori, A. Haghighi Asl, F. Hormozi
    . 2009, 17(3):  359-365. 
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    Mechanisms that control the extraction rate of essential oil from Zataria multiflora Boiss. (Z. multiflora) with subcritical water (SW) were studied. The extraction curves at different solvent flow rates were used to determine whether the extractions were limited primarily by the near equilibrium partitioning of the analyte between the matrix and solvent (i.e. partitioning thermodynamics) or by the rates of analyte desorption from the matrix (i.e. kinetics). Four simple models have been applied to describe the extraction profiles obtained with SW:(1) a model based solely on the thermodynamic distribution coefficient KD, which assumes that analyte desorption from the matrix is rapid compared to elution;(2) one-site kinetic model, which assumes that the extraction rate is limited by the analyte desorption rate from the matrix, and is not limited by the thermodynamic (KD) partitioning that occurs during elution;(3) two-site kinetic model and (4) external mass transfer resistance model. For SW extraction, the thermodynamic elution of analytes from the matrix was the prevailing mechanism as evidenced by the fact that extraction rates increased proportionally with the SW flow rate. This was also confirmed by the fact that simple removal calculations based on determined KD (for major essential oil compounds) gave good fits to experimental data for flow rates from 1 to 4 ml·min-1. The results suggested that the overall extraction mechanism was influenced by solute partitioning equilibrium with external mass transfer through liquid film.
    Prediction of Effective Diffusion Coefficient in Rotating Disc Columns and Application in Design
    Marzieh Amanabadi, Hossein Bahmanyar, Zohreh Zarkeshan, Mohamad Ali Mousavian
    . 2009, 17(3):  366-372. 
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    A rotating disc column (RDC) with inner diameter 68 mm and 28 compartments is used in this study. Parameters including Sauter mean diameter, hold-up and mass transfer coefficient are measured experimentally under different operating conditions. The correlations in literature for molecular diffusion and enhancement factor equation including eddy diffusion, circulation and oscillation of drops are evaluated. A new equation for the effective diffusion coefficient as a function of Reynolds number is proposed. The calculated values of mass transfer coefficient and column height from the previous equations and present equation are compared with the experimental data. The results from the present equation are in very good agreement with the experimental results, which may be used in designing RDC columns.
    催化、动力学与反应工程
    Combination of Supercritical Fluid Extraction with Ultrasonic Extraction for Obtaining Sex Hormones and IGF-1 from Antler Velvet
    周冉, 李淑芬, 张大成
    Chinese Journal of Chemical Engineering. 2009, 17(3):  373-380. 
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    Supercritical CO2 (SC-CO2) extraction technology and ultrasonic technology were used to extract two active sex hormones, estradiol and progesterone, and insulin-like growth factor-1 (IGF-1) from antler velvet. The effects of SC-CO2 extraction condition on the extraction yield and content of sex hormones, the ultrasonic extraction condition on the content of IGF-1 and the SC-CO2 extraction condition on the activity remaining of IGF-1 were studied. The optimal conditions were obtained. The experimental results showed that, in presence of 75% ethanol as the co-solvent, the mean yield and content of estradiol and progesterone were 87.67 pg·g-1 and 1224.10 pg·g-1, 12.38 ng·g-1 and 354.06 ng·g-1, respectively, with extraction pressure of 30 MPa, temperature of 35℃, extraction time of 30 min and CO2 consumption of 15 L·g-1 at the flow rate of 2.0 L·min-1. The highest content of IGF-1 was 7425.75 ng·g-1 antler velvet residue, when the pH10 ammonia-ammonium chloride buffer solution was used as the solvent, the ratio of solvent to sample was 20/1 (volume/mass), the extraction temperature was 0-35℃, and the extraction time was 4×15 min. Under these conditions, 93.68% activity remaining of IGF-1 in the residue was obtained, while little IGF-1 activity exists in traditional residue. The experimental results indicate that the technology of SC-CO2 with co-solvent is of advantage for getting high content sexual hormones and keeping high activity of IGF-1 in the residue, which can not be achieved by traditional extraction methods.
    CFD Simulation of Flow and Mass Transfer in Structured Packing Distillation Columns
    陈江波, 刘春江, 袁希钢, 余国琮
    Chinese Journal of Chemical Engineering. 2009, 17(3):  381-388. 
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    Detailed investigation of flow behavior in structured packing distillation columns is of great importance in accurate prediction of process efficiency and development of more efficient and optimal equipment internals. In this study, a three-dimensional two-phase flow model based on VOF method for simulating the hydrodynamics and mass-transfer behavior in a typical representative unit of the structured packing is developed. In the proposed model, the c2c model is used for the closure of turbulent mass transfer equation. By solving the proposed model, the velocity distribution, phase fraction profile and concentration field are obtained. Using these data, the total liquid holdup, the wetted area and the separation efficiency [height equivalent to a theoretical plate (HETP)] are estimated. For testing the model validation, the simulated HETPs are compared with our previous experimental data obtained in a 150 mm-diameter column containing Mellapak 350Y operating at the pressures of 0.6-1.8 MPa. The comparison shows that they are in satisfactory agreement, with an average absolute deviation (AAD) of 25.4%.
    Process Intensification of VOC Removal from High Viscous Media by Rotating Packed Bed
    李沃源, 毋伟, 邹海魁, 初广文, 邵磊, 陈建峰
    . 2009, 17(3):  389-393. 
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    The removal of a volatile organic compound (VOC) from high viscous liquid was carried out in a rotating packed bed (RPB) in this study. The mixed liquid of syrup and acetone was used as simulated high viscous polymer solution with acetone as the volatile compound. The influence of the rotating speed of RPB, liquid viscosity, liquid flow rate, vacuum degree, and initial acetone content in the liquid on acetone removal efficiency was investigated. The experimental results indicated that the removal efficiency increased with increasing rotating speed and initial acetone content in the viscous liquid and decreased with increasing liquid viscosity and flow rate. It was also observed that acetone removal efficiency increased with an increasing vacuum degree and reached 58% at a vacuum degree of 0.1 MPa. By the comparison with a flash tank devolatilizer, it was found that acetone removal efficiency in RPB increased by about 67%.
    Quantum Chemistry Studies on the Free-radical Growth Mechanism of Polycyclic Arenes from Benzene Precursors
    章日光, 王宝俊, 田亚峻, 凌丽霞
    . 2009, 17(3):  394-400. 
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    The free-radical growth mechanisms for the formation of polycyclic arenes (PCAs) were constructed based on the block unit of benzene, and were calculated by the quantum chemistry PM3 method. Two kinds of reaction paths are proposed and discussed. The calculation results show that the formation of PCAs is only controlled by the elimination of H atom from benzene, and the corresponding activation energy is 307.60 kJ·mol-1. H2 is only the effluent gas in our proposed reaction mechanism, and the calculation results are in accord with the experimental facts.
    Effect of Doping Cerium in the Support of Catalyst Pd-Co/Cu-Co-Mn Mixed Oxides on the Oxidative Carbonylation of Phenol
    梁英华, 郭红霞, 陈红萍, 吕敬德, 张波波
    . 2009, 17(3):  401-406. 
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    Effect of doping cerium in the support on the catalytic activity and side product of the reaction in the oxidative carbonylation of phenol to diphenyl carbonate (DPC) over the catalyst Pd-Co/Cu-Co-Mn mixed oxides was studied. The specific surface areas, crystal phase, valency, and content of the element on the surface of the catalysts were determined, and the products were detected by gas chromatograph/mass spectrometry (GC-MS). It is found that the catalyst without Ce shows higher activity than that with Ce, and the yields of DPC for the two catalysts can reach 30% and 23%, respectively. However, doping cerium can prevent the formation of 2-hydroxyphenyl benzoate and p-bromophenyl phenyl carbonate.
    Catalytic Oxidation of Cyclohexane over ZSM-5 Catalyst in N-alkyl-N-methylimidazolium Ionic Liquids
    胡永琪, 王建英, 赵瑞红, 刘玉敏, 刘润静, 李永丹
    . 2009, 17(3):  407-411. 
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    Heterogeneous oxidation of cyclohexane by tert-butyl hydroperoxide (TBHP) was carried out over ZSM-5 catalysts with different Si/Al ratios in ionic liquids and organic molecular solvents. Higher yield and selectivity of the desired products were found in ionic liquids than in molecular solvents. The conversion of cyclohexane exhibits a decrease from 15.8% to 10.8% with the increase of Si/Al ratio of the HZSM-5 catalyst, and all the catalysts exhibit good selectivity of monofunctional oxidation products at around 97%. The activity of catalyst is found strongly dependent on the alkyl chain length of ionic liquid.
    Investigation of Nitration Processes of iso-Octanol with Mixed Acid in a Microreactor
    沈佳妮, 赵玉潮, 陈光文, 袁权
    . 2009, 17(3):  412-418. 
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    In this paper, the nitration characteristic of alcohols with mixed acid for the synthesis of energetic materials in a stainless steel microreactor was investigated experimentally. The nitration of iso-octanol with HNO3-H2SO4 mixed acid was chosen as a typical model reaction which involved fast and strong exothermic liquid-liquid heterogeneous reaction process. The influences of mixed acid composition, flow rate, organic/aqueous flow ratio and reaction temperature have been investigated. The results indicated that the reaction could be conducted safely and stably in the microreactor at 25-40℃, which are enhanced compared to 15℃ or below for safe operating conditions in the conventional reactors. Moreover, the 98.2% conversion of iso-octanol could be obtained and no by-products were detected in all cases.
    Kinetic and Microstructure of SiC Deposited from SiCl4-CH4-H2
    杨艳, 张伟刚
    . 2009, 17(3):  419-426. 
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    Silicon carbide was prepared from SiCl4-CH4-H2 gaseous precursors by isothermal, isobaric chemical vapor deposition (CVD) at atmospheric pressure and temperatures ranging from 900℃ to 1100℃. Kinetic studies showed that carbosilane of SiH2Cl2, SiHCl3 and SiCl2 formed from decomposition of SiCl4 and CH4 contributed to the deposition of hexangular facet and granular pebble structured SiC. An average apparent activation energy of 152 kJ·mol-1 was determined. The overall CVD process was controlled not only by the surface reactions but also by complex gas phase reactions. The as-deposited thin film was characterized using scanning electron microscopy, X-ray diffraction and transmission electron microscopy, these analysis showed that the deposited thin film consisted of pure phase of the β-SiC, the growth morphology of β-SiC differs from hexangular facet to granular pebble structures, which varied with substrate length and CVD temperature.
    A Novel Systematic Method of Quality Monitoring and Prediction Based on FDA and Kernel Regression
    张曦, 马思乐, 阎威武, 赵旭, 邵惠鹤
    . 2009, 17(3):  427-436. 
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    A novel systematic quality monitoring and prediction method based on Fisher discriminant analysis (FDA) and kernel regression is proposed. The FDA method is first used for quality monitoring. If the process is under normal condition, then kernel regression is further used for quality prediction and estimation. If faults have occurred, the contribution plot in the fault feature direction is used for fault diagnosis. The proposed method can effectively detect the fault and has better ability to predict the response variables than principle component regression (PCR) and partial least squares (PLS). Application results to the industrial fluid catalytic cracking unit (FCCU) show the effectiveness of the proposed method.
    Modeling of Isomerization of C8 Aromatics by Online Least Squares Support Vector Machine
    李丽娟, 苏宏业, 褚建
    . 2009, 17(3):  437-444. 
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    The least squares support vector regression (LS-SVR) is usually used for the modeling of single output system, but it is not well suitable for the actual multi-input-multi-output system. The paper aims at the modeling of multi-output systems by LS-SVR. The multi-output LS-SVR is derived in detail. To avoid the inversion of large matrix, the recursive algorithm of the parameters is given, which makes the online algorithm of LS-SVR practical. Since the computing time increases with the number of training samples, the sparseness is studied based on the projection of online LS-SVR. The residual of projection less than a threshold is omitted, so that a lot of samples are kept out of the training set and the sparseness is obtained. The standard LS-SVR, nonsparse online LS-SVR and sparse online LS-SVR with different threshold are used for modeling the isomerization of C8 aromatics. The root-mean-square-error (RMSE), number of support vectors and running time of three algorithms are compared and the result indicates that the performance of sparse online LS-SVR is more favorable.
    Simultaneously Designing and Targeting for Networks with Multiple Resources of Different Qualities
    刘智勇, 李艳梅, 张广林, 杨玉桢
    . 2009, 17(3):  445-453. 
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    This paper presents a new design procedure for the networks with multiple resources, such as hydrogen and water, of different qualities. The minimum consumption targets of the resources and pinch-causing sources can be identified as well during design. The objective of this work is to reduce the consumption of the resources with higher quality due to their higher cost. A few examples are investigated to show the proposed method. For a network of single resource with single contaminant, there is often only one pinch point for the resource. On the other hand, for a network of multiple resources with single contaminant, there might be a few different pinch points. Each resource might have its own pinch point, if its amount is sufficient. The contaminant concentration of the pinch-causing source for a resource with lower concentration will be below that of the higher-concentration resource(s).
    Modeling and Control of Nonlinear Discrete-time Systems Based on Compound Neural Networks
    张燕, 梁秀霞, 杨鹏, 陈增强, 袁著祉
    . 2009, 17(3):  454-459. 
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    An adaptive inverse controller for nonliear discrete-time system is proposed in this paper. A compound neural network is constructed to identify the nonlinear system, which includes a linear part to approximate the nonlinear system and a recurrent neural network to minimize the difference between the linear model and the real nonlinear system. Because the current control input is not included in the input vector of recurrent neural network (RNN), the inverse control law can be calculated directly. This scheme can be used in real-time nonlinear single-input single-output (SISO) and multi-input multi-output (MIMO) system control with less computation work. Simulation studies have shown that this scheme is simple and affects good control accuracy and robustness.
    Gross Error Detection and Identification Based on Parameter Estimation for Dynamic Systems
    姜春阳, 邱彤, 赵劲松, 陈丙珍
    . 2009, 17(3):  460-467. 
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    The detection and identification of gross errors, especially measurement bias, plays a vital role in data reconciliation for nonlinear dynamic systems. Although parameter estimation method has been proved to be a powerful tool for bias identification, without a reliable and efficient bias detection strategy, the method is limited in efficiency and cannot be applied widely. In this paper, a new bias detection strategy is constructed to detect the presence of measurement bias and its occurrence time. With the help of this strategy, the number of parameters to be estimated is greatly reduced, and sequential detections and iterations are also avoided. In addition, the number of decision variables of the optimization model is reduced, through which the influence of the parameters estimated is reduced. By incorporating the strategy into the parameter estimation model, a new methodology named IPEBD (Improved Parameter Estimation method with Bias Detection strategy) is constructed. Simulation studies on a continuous stirred tank reactor (CSTR) and the Tennessee Eastman (TE) problem show that IPEBD is efficient for eliminating random errors, measurement biases and outliers contained in dynamic process data.
    Position Group Contribution Method for Estimation of Melting Point of Organic Compounds
    王强, 马沛生, 能士峰
    . 2009, 17(3):  468-472. 
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    A new method is proposed based on the position group contribution additivity for the prediction of melting points of covalent compounds. The characteristics of this method are the use of position distribution function, which could distinguish between most isomers including cis or trans structure of organic compounds. Contributions for hydrocarbons and hydrocarbon derivatives containing oxygen, nitrogen, chlorine, bromine and sulfur, are given. Results are compared with those by the most commonly used estimating methods. The average derivation for prediction of normal melting temperature of 730 compounds is 14.46 K, compared to 29.33 K with the method of Joback, and 27.81 K with the method of Constantinou-Gani. The present method is not only more accurate, but also much simpler and more stable.
    Measurement and Correlation of Solubilities of Adipic Acid in Different Solvents
    毛治博, 孙晓波, 栾向海, 王钰, 刘国际
    . 2009, 17(3):  473-477. 
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    Using a simple and reliable apparatus, the solubilities of adipic acid in water, ethanol, chloroform, n-butanol and acetone are determined by the analytic method. The results are correlated with λh equation, Apelblat equation, and UNIFAC equation. The solubilities calculated by these models are in good agreement with experimental data, so that the models can meet the requirements of engineering design.
    Antioxidant and Antimicrobial Activities of Echinacea (Echinacea purpurea L.) Extracts Obtained by Classical and Ultrasound Extraction
    Ivana Stanisavljević, Saša Stojičević, Dragan Veličković, Vlada Veljković, Miodrag Lazić
    . 2009, 17(3):  478-483. 
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    Antioxidant and antimicrobial activities of Echinacea purpurea L. (Asteraceae) extracts obtained by classical and ultrasound solvent extraction were compared. The dry aerial part of plant was extracted by 70% ethanol at a solid-to-liquid ratio of 1:10 (m/v) and 25℃. The extract obtained by classical solvent extraction contained 29% larger amounts of phenolic compounds and 20% higher content of flavonoids. 2,2-diphenyl-1-picril hydrazyl radical (DPPH) scavenging reached 93.6% and the values of EC50 were (34.16±0.65)μg·ml-1 and (65.48±1.12) μg·ml-1 for the extracts obtained by the classical and ultrasound extractions, respectively. The extracts, independent of the extraction technique applied, showed a considerable growth inhibition on Candida albicans and Saccharomyces cerevisiae, while no growth inhibition zones were observed for Aspergillus niger. The diameters of inhibition zone observed for all the microorganisms were larger for extracts obtained by classical extraction than those by ultrasound extraction.
    On-line Monitoring for Phosphorus Removal Process and Bacterial Community in Sequencing Batch Reactor
    崔有为, 王淑莹, 李晶
    . 2009, 17(3):  484-492. 
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    For efficient energy consumption and control of effluent quality, the cycle duration for a sequencing batch reactor (SBR) needs to be adjusted by real-time control according to the characteristics and loading of wastewater. In this study, an on-line information system for phosphorus removal processes was established. Based on the analysis for four systems with different ecological community structures and two operation modes, anaerobic-aerobic process and anaerobic-anaerobic process, the characteristic patterns of oxidation-reduction potential (ORP) and pH were related to phosphorous dynamics in the anaerobic, anoxic and aerobic phases, for determination of the end of phosphorous removal. In the operation mode of anaerobic-aerobic process, the pH profile in the anaerobic phase was used to estimate the relative amount of phosphorous accumulating organisms (PAOs) and glycogen accumulating organisms (GAOs), which is beneficial to early detection of ecology community shifts. The on-line sensor values of pH and ORP may be used as the parameters to adjust the duration for phosphorous removal and community shifts to cope with influent variations and maintain appropriate operation conditions.
    Reaction Characteristics of Asymmetric Synthesis of (2S,5S)-2,5-Hexanediol Catalyzed with Baker’s Yeast Number 6
    肖美添, 叶静, 张亚武, 黄雅燕
    . 2009, 17(3):  493-499. 
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    Baker’s yeast number 6 was selected by screening. It showed good catalytic activity and enantioselectivity for asymmetric reduction of 2,5-hexanedione to produce (2S,5S)-2,5-hexanediol. Gas chromatography-mass spectrometry (GC-MS) revealed that the intermediate was (S)-5-hydroxyhexane-2-one. Reduction of 2,5-hexanedione proceeded in a two-step reaction. The hydroxyketone was initially formed, and this intermediate was further reduced to the diol. Factors influencing the product yield and the enantiomeric excess of the reduction of 2,5-hexandione catalyzed by baker’s yeast number 6 were investigated. Higher concentration (≤100 mmol·L-1) of 2,5-hexandione did not influence 5-hydroxyhexane-2-one production, but 2,5-hexanediol production was inhibited by excess accumulation (>30 mmol·L-1) of intermediate. The optimal conditions were glucose as the co-substrate at an initial glucose concentration of 20 g·L-1, 34℃, pH 7.0 and cell concentration 60 g·L-1 (cell dry mass). Under the optimal condition and an initial substrate concentration of 30 mmol·L-1, the yield of 2,5-hexandiol was 78.7% and the enantiomeric excess of (2S,5S)-2,5-hexandiol was 94.4% for 24-h reduction.
    Biodegradation of Aniline by a Newly Isolated Delftia sp. XYJ6
    肖诚斌, 宁君, 闫海, 孙旭东, 胡继业
    . 2009, 17(3):  500-505. 
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    A promising gram-negative bacterial strain for the biodegradation of aniline as the sole carbon, nitrogen and energy sources was successfully isolated and identified as Delftia sp. XYJ6. The optimal temperature and pH for both the growth of Delftia sp. XYJ6 and the biodegradation of aniline were 30℃ and 7.0, respectively. Initial aniline of 2000 mg·L-1 could be completely removed by the strain at 22 h, which showed that Delftia sp. XYJ6 had a strong ability in the biodegradation of aniline. It indicated that aniline was firstly converted to catechol catalyzed by aniline dioxygenase as a first product, which was then further biodegraded to cis,cis-muconic acid catalyzed by the catechol 1,2-dioxygenase of Delftia sp. XYJ6 as a second product. Cis,cis-muconic acid could also be further biodegraded to other small compound again. The pathway for the biodegradation of aniline by Delftia sp. XYJ6 was not previously reported.
    Resolution of Ibuprofen Ester by Catalytic Antibodies in Water-miscible Organic-solvents
    杨根生, 应黎, 欧志敏, 姚善泾
    . 2009, 17(3):  506-512. 
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    The asymmetric hydrolysis of racemic ibuprofen ester is one of the most important methods for chiral separation of ibuprofen. In this work, a catalytic antibody that accelerates the rate of enantioselective hydrolysis of ibuprofen methyl ester was obtained against an immunogen consisting of tetrahedral phosphonate hapten attached to bovine serum albumin (BSA). The catalytic activity of the catalytic antibody in the water-miscible organic-solvent system composed of a buffer solution and N, N-dimethylformamide (DMF) was studied. With 6% DMF in the buffer solution (containing catalytic antibody 0.25 μmol, 0.2 mol·L-1 phosphate buffer, pH 8) at 37℃ for 10 h, a good conversion (48.7%) and high enantiomeric excess (>99%) could be reached. The kinetic analysis of the catalytic antibody-catalyzed reaction showed that the hydrolysis in the water-miscible organic-solvent system with DMF in buffer solution followed the Michaelis-Menten kinetics. The catalytic efficiency (Kcat/Km) was enhanced to 151.91 L·mmol-1·min-1, twice as large as that for the buffer solution only.
    Adsorption of Dye from Wastewater by Zeolites Synthesized from Fly Ash:Kinetic and Equilibrium Studies
    王春峰, 李健生, 王连军, 孙秀云, 黄佳佳
    . 2009, 17(3):  513-521. 
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    The removal performance of a basic dye, methylene blue (MB), in aqueous solution was investigated by adsorption process on single-phase and high-crystalline zeolite A (FA-ZA) and X (FA-ZX). Both adsorbents FA-ZA and FA-ZX were synthesized from fly ash prepared aluminosilicate gel followed by the hydrothermal treatment at 100℃ with the control of Si/Al molar ratio, respectively. The properties of the synthetic zeolites and commercial grade zeolites, such as thermal stability, elemental composition, and cation exchange capacity, were investigated for comparison. Batch method was used to study the influential parameters, such as initial pH value of the solution, temperatures, and adsorbents dosage, on the adsorption process. The experimental data were well fitted by Ho’ pseudo-second-order model and liquid film diffusion model. The suitability of Langmuir and Freundlich isotherms to the equilibrium data was investigated in the solid-liquid system while the Langmuir model produces the best results. Thermodynamic data (△H, △S, and △G) corresponding to the MB uptake were evaluated from the Langmuir model. In all the adsorption experiments, the adsorption capacity followed the order as follows:FA-ZX>FA-ZA. In addition, attempts were also made to regenerate the adsorbents.
    Mechanism Study of Rice Straw Pyrolysis by Fourier Transform Infrared Technique
    付鹏, 胡松, 向军, 孙路石, 杨涛, 张安超, 张军营
    . 2009, 17(3):  522-529. 
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    The pyrolysis mechanism of rice straw (RS) was investigated using a tube reactor with Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analyzer. The results show that the maximum pyrolysis rate increases with increasing heating rate and the corresponding temperature also increases. The three-pseudocomponent model could describe the pyrolysis behavior of rice straw accurately. The main pyrolysis gas products are H2O, CO2, CO, CH4, HCHO(formaldehyde), HCOOH (formic acid), CH3OH (methanol), C6H5OH (phenol), etc. The releasing of H2O, CO2, CO and CH4 mainly focuses at 220-400℃. The H2O formation process is separated into two stages corresponding to the evaporation of free water and the formation of primary volatiles. The release of CO2 first increases with increasing temperature and gets the maximum at 309℃. The releasing behavior of CO is similar to H2O and CO2 between 200 and 400℃. The production of CH4 happens, compared to CO2 and CO, at higher temperatures of 275-400℃ with the maximum at 309℃. When the temperature exceeds 200℃, hydroxyl and aliphatic C—H groups decrease significantly, while C—O, olefinic C—C bonds and ether structures increase first in the chars and then the aromatic structure develops with rising temperature. Above 500℃, the material becomes increasingly more aromatic and the ether groups decreases with an increase of temperature. The aromatization process starts at ≈350℃ and continues to higher temperatures.
    Novel High Performance Ziegler-Natta Catalyst for Ethylene Slurry Polymerization
    郭子芳, 陈伟, 周俊领, 杨红旭
    . 2009, 17(3):  530-534. 
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    A novel high performance MgCl2/TiCl4 catalyst with tetrabutyloxsilicane as electron donor was prepared for ethylene slurry polymerization process. The properties of the catalyst such as particle size distribution, catalytic activity, hydrogen responsibility and copolymerization performance were investigated and compared with commercial catalyst (imported catalyst). Copolymerization of ethylene and 1-butylene using the catalyst was studied in a pilot plant. The composition, structure and property of the copolymer were characterized by 13C nuclear magnetic resonance (13C NMR) and gel permeation chromatography-Infrared (GPC-IR), and compared with those of the copolymer obtained from a commercial catalyst. In comparison with the commercial catalyst, the novel catalyst had a higher activity (up to 34.6 kg·g-1) and a better particle size distribution (PSD), and produced polymers having higher bulk density (up to 0.37 g·cm-3) with less fine resin. Meanwhile, the novel catalyst showed a higher hydrogen responsibility and better copolymerization performance. The results indicated that the copolymer obtained from the novel catalyst has a higher branch in the high molecular weight fraction and lower branch in the low molecular weight fraction.