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SCI和EI收录∣中国化工学会会刊
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Table of Content
28 March 2013, Volume 21 Issue 3
    SEPARATION SCIENCE AND ENGINEERING
    Removal of Lead Ions from Ginseng Ethanol Extracts by Dynamic Adsorption in a Fixed-bed Column
    LIU Wenfang, ZHAO Zhiping, GUO Yiqiong
    2013, 21(3):  227-231.  doi:10.1016/S1004-9541(13)60472-3
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    The removal of lead from ginseng ethanol extracts by a fixed-bed column filled with an adsorbent bearing amine and carboxyl groups was investigated. The Pb2+ content was determined by inductively coupled plasma mass spectrometry. When the flowrate increased from 0.12 to 0.34 ml•min-1, the column exhibited a marked increase in percentage of lead removal from 54.9% to 92.3%. Further increase in the flowrate did not bring evident changes to the lead removal, whereas an increase in the temperature could reinforce adsorption further, suggesting that the adsorption process was controlled by external film diffusion below the flowrate of 0.34 ml•min-1, and by the intraparticle pore diffusion of lead ions when the flowrate exceeded it. A low remaining lead amount in extracts such as 0.11 mg•kg-1 (extracts powder) was achieved. The adsorbents also adsorbed effective constituents to some extent. But 88% of constituents adsorbed were taken off using a 70% ethanol aqueous solution.
    Permeation Characteristics of Light Hydrocarbons Through Poly(amide-6-β-ethylene oxide) Multilayer Composite Membranes
    REN Xiaoling, REN Jizhong, LI Hui, DENG Maicun
    2013, 21(3):  232-237.  doi:10.1016/S1004-9541(13)60462-0
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    In this paper, poly(amide-6-β-ethylene oxide) (PEBA1657) copolymer was used to prepare multilayer polyetherimide (PEI)/polydimethylsiloxane (PDMS)/PEBA1657/PDMS composite membranes by dip-coating method. Permeation behaviors of ethylene, ethane, propylene, propane, n-butane, methane and nitrogen through the multilayer composite membranes were investigated over a range of operating temperature and pressure. The permeances of light hydrocarbons through PEI/PDMS/PEBA1657/PDMS composite membranes increase with their increasing condensability, and the olefins are more permeable than their corresponding paraffins. For light hydrocarbons, the gas permeances increase significantly as temperature increasing. When the transmembrane pressure difference increases, the gas permeance increases moderately due to plasticization effect, while their apparent activation energies for permeation decrease.
    CATALYSIS, KINETICS AND REACTION ENGINEERING
    Numerical Analysis on the Characteristics of Soot Particles in C2H4/CO2/O2/N2 Combustion
    LI Shanling, JIANG Yong, CHEN Wenting
    2013, 21(3):  238-245.  doi:10.1016/S1004-9541(13)60485-3
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    The purpose of this study is to investigate the characteristics of soot particles in C2H4/CO2/O2/N2 combustion at equivalence ratio of 3.0-5.0. As the oxidant is switched from conventional air to CO2/O2/N2 mixture, the key species C2H2, C3H3 responsible for formation of first aromatic ring, the typical aromatics and 4-ring aromatics total production rate all decrease greatly. In addition, with CO2 mole fraction from 0.2 to 0.5 in the mixture, the soot particle number density, volume fraction, surface area density, which are three most important parameters to soot particle property, are suppressed obviously. Furthermore, the increasing content of CO2 in the oxidizer influences mostly H, OH radical concentrations by two reactions: CO+OH=CO2 H and H+O2=O+OH, and the production rate of H, OH from the two reactions declined, which revealed that CO2 in mixture has an inhibiting effect on soot particle generation.
    Simulation of Continuous Esterification Process of Polyester Polyols
    CHEN Like, XI Zhenhao, QIN Zhen, ZHAO Ling, YUAN Weikang
    2013, 21(3):  246-252.  doi:10.1016/S1004-9541(13)60472-6
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    Based on the kinetic and thermodynamic equations, a comprehensive mathematical model for the continuous esterification process of polyester polyols was developed, which was carried out in an innovational bubbling reactive distillation tower (BRDT) at atmospheric pressure. In this new type of reactor, direct esterification between ethylene glycol and adipic acid was accomplished efficiently and rapidly. A bench BRDT with the height of 2 m was applied for the esterification process of poly (ethylene adipate) (PEA). In the continuous operation, linear oligomers were discharged from the bottom of the column, while water passed a few column trays and a packing section as a condensation byproduct. The influence of major operating conditions on reactor performance was also simulated. Simulation results were in good agreement with experimental data, providing a strategy for developing and optimizing this process.
    PROCESS SYSTEMS ENGINEERING
    Analysis on Refinery System as a Complex Task-resource Network
    LIU Suyu, RONG Gang
    2013, 21(3):  253-262.  doi:10.1016/S1004-9541(13)60485-1
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    the resources exchanged among tasks. Using the properties of node degree distribution, strength distribution and other weighted quantities, we demonstrate the heterogeneity of the network and point out the relation between structural characters of vertices and the functionality of corresponding tasks. The above phenomena indicate that the design requirements and principles of production process contribute to the heterogeneous features of the network. Besides, betweenness centrality of nodes can be used as an importance indicator to provide additional information for decision making. The correlations between structure and weighted properties are investigated to further address the influence brought by production schemes in system connectivity patterns. Cascading failures model is employed to analyze the robustness of the network when targeted attack happens. Two capacity assignment strategies are compared in order to improve the robustness of the network at certain cost. The refinery system displays more reliable behavior when the protecting strategy considers heterogeneous properties. This phenomenon further implies the structure-activity relationship of the refinery system and provides insightful suggestions for process system design. The results also indicate that robustness analysis is a promising application of methodologies from complex networks to process system engineering.
    On-line Batch Process Monitoring with Improved Multi-way Independent Component Analysis
    GUO Hui, LI Hongguang
    2013, 21(3):  263-270.  doi:10.1016/S1004-9541(13)60485-4
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    In the past decades, on-line monitoring of batch processes using multi-way independent component analysis (MICA) has received considerable attention in both academia and industry. This paper focuses on two troublesome issues concerning selecting dominant independent components without a standard criterion and determining the control limits of monitoring statistics in the presence of non-Gaussian distribution. To optimize the number of key independent components, we introduce a novel concept of system deviation, which is able to evaluate the reconstructed observations with different independent components. The monitored statistics are transformed to Gaussian distribution data by means of Box-Cox transformation, which helps readily determine the control limits. The proposed method is applied to on-line monitoring of a fed-batch penicillin fermentation simulator, and the experimental results indicate the advantages of the improved MICA monitoring compared to the conventional methods.
    An Anticipatory Terminal Iterative Learning Control Approach with Applications to Constrained Batch Processes
    CHI Ronghu, ZHANG Dexia, LIU Ximei, HOU Zhongsheng, JIN Shangtai
    2013, 21(3):  271-275.  doi:10.1016/S1004-9541(13)60485-2
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    This work presents an anticipatory terminal iterative learning control scheme for a class of batch processes, where only the final system output is measurable and the control input is constant in each operations. The proposed approach works well with input constraints provided that the desired control input with respect to the desired trajectory is within the saturation bound. The tracking error convergence is established with rigorous mathematical analysis. Simulation results are provided to show the effectiveness of the proposed approach.
    Bypass Selection for Control of Heat Exchanger Network
    SUN Lin, LUO Xionglin, HOU Benquan, BAI Yujie
    2013, 21(3):  276-284.  doi:10.1016/S1004-9541(13)60472-5
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    Considering the flexibility and controllability of heat exchanger networks (HENs), bypasses are widely used for effective control of process stream target temperatures. However, the optimal location for the bypass is generally difficult to design with the trade-off between controllability and capital investments. In this paper, based on the steady-state model of heat exchanger networks the optimal bypass location was firstly selected by iteratively calculating the non-square Relative Gain Array (ns-RGA). To simplify the calculation process, rules of bypass selection were also proposed. In order to evaluate this method, then, the structural controllability of heat exchanger networks was analyzed. With both the consideration of the controllability and capital investments, the bypasses locations were finally selected. A case study on the HEN in Crude Distillation Unit was presented in which the ns-RGA and structural controllability were used to select bypasses and also to evaluate the results.
    A Novel Strategy for Simulating the Main Fractionator of Delayed Cokers by Separating the De-superheating Process
    LEI Yang, ZHANG Bingjian, HOU Xiaoqiong, CHEN Qinglin
    2013, 21(3):  285-294.  doi:10.1016/S1004-9541(13)60472-4
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    Delayed coking is an important process in refinery to convert heavy residue oils from crude distillation units (CDUs) and fluid catalytic cracking units (FCCUs) into dry gas, liquefied petroleum gas (LPG), gasoline, diesel, gas oils and cokes. The main fractionator, separating superheating reaction vapors from the coke drums into lighter oil products, involves a de-superheating section and a rectifying section, and couldn't be simulated as a whole column directly because of non-equilibrium in the de-superheating section. It is very important to correctly simulate the main fractionator for operational parameter and energy-use optimization of delayed cokers. This paper discusses the principle of de-superheating processes, and then proposes a new simulation strategy. Some key issues such as composition prediction of the reaction vapors, selection of thermodynamic methods, estimation of tray efficiency, etc. are discussed. The proposed simulation approach is applied to two industrial delayed cokers with typical technological processes in a Chinese refinery by using PRO/II. The simulation results obtained are well consistent with the actual operation data, which indicates that the presented approach is suitable to simulate the main fractionators of delayed cokers or other distillation columns consisting of de-superheating sections and rectifying sections.
    CHEMICAL ENGINEERING THERMODYNAMICS
    Kinetic and Phase Behaviors of Catalytic Cracking Dry Gas Hydrate in Water-in-Oil Emulsion
    MA Qinglan, HUANG Qiang, CHEN Guangjin, WANG Xiulin, SUN Changyu, YANG Lanying
    2013, 21(3):  295-300.  doi:10.1016/S1004-9541(13)60466-8
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    The systematic experimental studies were performed on the hydrate formation kinetics and gas-hydrate equilibrium for a simulated catalytic cracking gas in the water-in-oil emulsion. The effect of temperature, pressure and initial gas-liquid ratio on the hydrate formation was studied, respectively. The data were obtained at pressures ranging from 3.5 to 5 MPa and temperatures from 274.15 to 277.15 K. The results showed that hydrogen and methane can be separated from the C2+ fraction by forming hydrate at around 273.15 K which is much higher temperature than that of the cryogenic separation method, and the hydrate formation rate can be enhanced in the water-in-oil emulsion compared to pure water. The experiments provided the basic data for designing the industrial process, and setting the suitable operational conditions. The measured data of gas-hydrate equilibria were compared with the predictions by using the Chen-Guo hydrate thermodynamic model.
    Molecular Simulation of Oxygen Sorption and Diffusion in the Poly (lactic acid)
    SUN Delin, ZHOU Jian
    2013, 21(3):  301-309.  doi:10.1016/S1004-9541(13)60472-7
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    Grand canonical Monte Carlo and molecular dynamics simulation methods are used to simulate oxygen sorption and diffusion in amorphous poly(lactic acid) (PLA). The simulated solubility coefficient of oxygen is close to experimental data obtained from the quartz crystal microbalance but much higher than those from the time-lag method. This discrepancy is explained by using the dual-mode sorption model. It is found that oxygen sorption in PLA is predominantly Langmuir type controlled, em.e., through the process of filling holes. The time-lag method only takes into account oxygen molecules that participate the diffusion process whereas a large proportion of oxygen molecules trapped in the void have little chance to execute hopping due to the glassy nature of PLA at room temperature. The simulated diffusion coefficient of oxygen is reasonably close to the data obtained from the time-lag method. The solubility coefficient of oxygen decreases linearly with increasing relative humidity while its diffusion coefficient firstly decreases and then increases as a function of relative humidity.
    Solubility of CO2 in Methanol, 1-Octyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide, and Their Mixtures
    LEI Zhigang, ZHANG Benfeng, ZHU Jiqin, GONG Wanfu, L? Jianning, LI Yansheng
    2013, 21(3):  310-317.  doi:10.1016/S1004-9541(13)60464-4
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    Solubility data of carbon dioxide (CO2) (1) in methanol (2), 1-octyl-3-methylimidazolium bis(trifluoro- methylsulfonyl)imide ([omim]+[Tf2N]-) (3), and their mixtures (w3 0.2, 0.5, and 0.8) at temperatures 313.2 and 333.2 K and pressures up to 7.0 MPa were measured by a high-pressure view-cell technique. The solubility of CO2 in methanol (w3=0), [omim]+[Tf2N]- (w3=1.0) and their mixtures follows the order of (w3=0)<(w3=0.2)< (w3=0.5)<(w3=0.8)<(w3=1.0) at the same temperature and pressure, while the magnitude of Henry's constants follows the reverse order at a given temperature, which is consistent with the COSMO-RS (conductor-like screening for real solvents) calculation. The solubility data of CO2 in methanol and [omim]+[Tf2N]- are correlated with the Peng-Robinson equation of state, and the solubility of CO2 in the mixtures of methanol and [omim]+[Tf2N]- can be well predicted based on the mole fraction average of methanol and [omim]+[Tf2N]- over the solubility of CO2 in pure methanol and [omim]+[Tf2N]-. The mixtures of methanol and [omim]+[Tf2N]- may be used as physical solvents for capturing CO2 with high partial pressures since they combine the advantages of organic solvents and ionic liquids.
    ENERGY, RESOURCES AND ENVIRONMENTAL TECHNOLOGY
    Effects of Slow-Mixing on the Coagulation Performance of Polyaluminum Chloride (PACI)
    ZHANG Zhongguo, LIU Dan, HU Dandan, LI Duo, REN Xiaojing, CHENG Yanjun, LUAN Zhaokun
    2013, 21(3):  318-323.  doi:10.1016/S1004-9541(13)60463-2
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    Conventional jar tests and on-line size monitoring were used to investigate the effects of slow-mixing intensity and duration on residual turbidity and floc size during charge neutralization coagulation and sweep flocculation with polyaluminum chloride. The compensatory effect of slow-mixing on coagulation performance following inadequate or excessive rapid-mixing was also examined. It is found that slow-mixing intensity has a more marked positive effect on charge neutralization coagulation than on sweep flocculation. The optimal root-mean- square velocity gradient, G, for slow-mixing is 15 s-1 for both coagulation mechanisms, and charge neutralization coagulation requires a longer slow-mixing duration. The optimal slow-mixing duration, based on residual turbidity, is longer than the time to form the largest mean flocs. The optimal product of G and mixing duration, GT, for slow-mixing during charge neutralization coagulation (13500) are higher than that during sweep flocculation (4500) and both are less than the range of values recommended by the American Water Works Association (24000-84000). The optimal GT value under various slow-mixing conditions increases with G. Appropriate extension of slow-mixing duration during charge neutralization coagulation can improve coagulation performance after an inadequate or excessive rapid-mixing duration, but during sweep flocculation, appropriate shortening of slow-mixing duration after an excessive rapid-mixing or appropriate extension of slow-mixing duration after an inadequate rapid-mixing is favorable.
    Cooling of a Diesel Reformate Fuelled Solid Oxide Fuel Cell by Internal Reforming of Methane: A Modelling Study
    HUANG Xiaowei, Alexander Kromp
    2013, 21(3):  324-331.  doi:10.1016/S1004-9541(13)60485-5
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    In this paper a system combining a diesel reformer using catalytic partial oxidation (CPOX) with the Solid Oxide Fuel Cell (SOFC) for Auxiliary Power Unit (APU) applications is modeled with respect to the cooling effect provided by internal reforming of methane in anode gas channel. A model mixture consisting of 80% n-hexadecane and 20% 1-methylnaphthalin is used to simulate the commercial diesel. The modelling consists of several steps. First, equilibrium gas composition at the exit of CPOX reformer is modelled in terms oxygen to carbon (O/C) ratio, fuel utilization ratio and anode gas recirculation. Second, product composition, especially methane content, is determined for the methanation process at the operating temperatures ranging from 500 ℃ to 520 ℃. Finally, the cooling power provided by internal reforming of methane in SOFC fuel channel is calculated for two concepts to increase the methane content of the diesel reformate. The results show that the first concept, operating the diesel reformer at low O/C ratio and/or recirculation ratio, is not realizable due to high probability of coke formation, whereas the second concept, combining a methanation process with CPOX, can provide a significant cooling effect in addition to the conventional cooling concept which needs higher levels of excess air.
    Identification and Metabolic Mechanism of Non-fermentative Short-cut Denitrifying Phosphorus-removing Bacteria
    LIU Hui, SUN Yanfu, JIA Xiaoshan, LI Jun, ZHOU Kangqun, QU Xiangdong, TAO Xueqin, CHEN Yu
    2013, 21(3):  332-340.  doi:10.1016/S1004-9541(13)60465-6
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    To investigate the characteristics and metabolic mechanism of short-cut denitrifying phosphorus-removing bacteria (SDPB) that are capable of enhanced biological phosphorus removal (EBPR) using nitrite as an electron acceptor, an aerobic/anoxic sequencing batch reactor was operated under three phases. An SDPB-strain YC was screened after the sludge enrichment and was identified by morphological, physiological, biochemical properties and 16S rDNA gene sequence analysis. Denitrifying phosphorus-removing experiments were conducted to study anaerobic and anoxic metabolic mechanisms by analyzing the changes of chemical oxygen demand (COD), phosphate, nitrite, poly-β-hydroxybutyrate (PHB), and glycogen. The results show that strain YC is a non-fermentative SDPB similar to Paracoccus denitrificans. As a kind of non-fermentative bacteria, the energy of strain YC was mainly generated from phosphorus release (96.2%) under anaerobic conditions with 0.32 mg P per mg synthesized PHB. Under anoxic conditions, strain YC accumulated 0.45 mg P per mg degraded PHB, which produced most of energy for phosphate accumulation (91.3%) and a little for glycogen synthesis (8.7%). This metabolic mechanism of strain YC is different from that of traditional phosphorus-accumulating organisms (PAOs). It is also found that PHB, a kind of intracellular polymer, plays a very important role in denitrifying and accumulating phosphorus by supplying sufficient energy for phosphorous accumulation and carbon sources for denitrification. Therefore, monitoring ΔP/ΔPHB and? ΔNO2--N/ΔPHB is more necessary than monitoring ΔP/ΔCOD,?ΔNO2--N/ΔCOD, or ΔNO2--N.