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本期目录
2013年 第21卷 第3期 刊出日期:2013-03-28
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分离科学与工程
Removal of Lead Ions from Ginseng Ethanol Extracts by Dynamic Adsorption in a Fixed-bed Column
刘文芳, 赵之平, 郭轶琼
Chinese Journal of Chemical Engineering. 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 Pb
2+
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
任晓灵, 任吉中, 李晖, 邓麦村
Chinese Journal of Chemical Engineering. 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.
催化、动力学与反应工程
Numerical Analysis on the Characteristics of Soot Particles in C
2
H
4
/CO
2
/O
2
/N
2
Combustion
李山岭, 蒋勇, 陈文婷
Chinese Journal of Chemical Engineering. 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 C
2
H
4
/CO
2
/O
2
/N
2
combustion at equivalence ratio of 3.0-5.0. As the oxidant is switched from conventional air to CO
2
/O
2
/N
2
mixture, the key species C
2
H
2
, C
3
H
3
responsible for formation of first aromatic ring, the typical aromatics and 4-ring aromatics total production rate all decrease greatly. In addition, with CO
2
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 CO
2
in the oxidizer influences mostly H, OH radical concentrations by two reactions: CO+OH=CO
2
H and H+O
2
=O+OH, and the production rate of H, OH from the two reactions declined, which revealed that CO
2
in mixture has an inhibiting effect on soot particle generation.
Simulation of Continuous Esterification Process of Polyester Polyols
陈礼科, 奚桢浩, 秦榛, 赵玲, 袁渭康
Chinese Journal of Chemical Engineering. 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.
过程系统工程与过程安全
Analysis on Refinery System as a Complex Task-resource Network
刘苏昱, 荣冈
Chinese Journal of Chemical Engineering. 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
郭辉, 李宏光
Chinese Journal of Chemical Engineering. 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
池荣虎, 张德霞, 刘喜梅, 侯忠生, 金尚泰
Chinese Journal of Chemical Engineering. 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
孙琳, 罗雄麟, 侯本权, 白玉杰
Chinese Journal of Chemical Engineering. 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
雷杨, 张冰剑, 侯小琼, 陈清林
Chinese Journal of Chemical Engineering. 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.
化工热力学
Kinetic and Phase Behaviors of Catalytic Cracking Dry Gas Hydrate in Water-in-Oil Emulsion
马庆兰, 黄强, 陈光进, 王秀林, 孙长宇, 杨兰英
Chinese Journal of Chemical Engineering. 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 C
2+
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)
孙德林, 周健
Chinese Journal of Chemical Engineering. 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 CO
2
in Methanol, 1-Octyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide, and Their Mixtures
雷志刚, 张本凤, 朱吉钦, 宫万福, 吕建宁, 李延生
Chinese Journal of Chemical Engineering. 2013, 21(3): 310-317. doi:
10.1016/S1004-9541(13)60464-4
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Solubility data of carbon dioxide (CO
2
) (1) in methanol (2), 1-octyl-3-methylimidazolium bis(trifluoro- methylsulfonyl)imide ([omim]
+
[Tf
2
N]
-
) (3), and their mixtures (
w
3
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 CO
2
in methanol (
w
3
=0), [omim]
+
[Tf
2
N]
-
(
w
3
=1.0) and their mixtures follows the order of (
w
3
=0)<(
w
3
=0.2)< (
w
3
=0.5)<(
w
3
=0.8)<(
w
3
=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 CO
2
in methanol and [omim]
+
[Tf
2
N]
-
are correlated with the Peng-Robinson equation of state, and the solubility of CO
2
in the mixtures of methanol and [omim]
+
[Tf
2
N]
-
can be well predicted based on the mole fraction average of methanol and [omim]
+
[Tf
2
N]
-
over the solubility of CO
2
in pure methanol and [omim]
+
[Tf
2
N]
-
. The mixtures of methanol and [omim]
+
[Tf2N]
-
may be used as physical solvents for capturing CO
2
with high partial pressures since they combine the advantages of organic solvents and ionic liquids.
能源、资源与环境技术
Effects of Slow-Mixing on the Coagulation Performance of Polyaluminum Chloride (PACI)
张忠国, 刘丹, 胡丹丹, 李多, 任晓晶, 程言君, 栾兆坤
Chinese Journal of Chemical Engineering. 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
黄肖微, Alexander Kromp
Chinese Journal of Chemical Engineering. 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
刘晖, 孙彦富, 贾晓珊, 李军, 周康群, 屈向东, 陶雪琴, 陈瑜
Chinese Journal of Chemical Engineering. 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? ΔNO
2
-
-N/ΔPHB is more necessary than monitoring ΔP/ΔCOD,?ΔNO
2
-
-N/ΔCOD, or ΔNO
2
-
-N.
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