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Table of Content
05 April 2016, Volume 35 Issue 04
    Invited reviews
    Pioneering application of biological process engineering in innovative bio-pharmaceutical development——bioreactors
    SUN Yang, NIE Jianqi, LIU Xiuxia, YANG Yankun, DAI Xiaofeng, BAI Zhonghu
    2016, 35(04):  971-980.  doi:10.16085/j.issn.1000-6613.2016.04.001
    Abstract ( 749 )   PDF (19616KB) ( 382 )  
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    In recent years, the proportion of innovative biomedical in the biotechnology industry has been increasing gradually, which is mainly due to the improvement of upstream technology such as target screening and molecule construction and brings tremendous economic benefit. With the increasing applications of cell culture technology in biomedical industry, demand for its innovation has been increasing. And so it is with the equipment bioreactors. This review introduced the categories, development trend and driving force of bioreactors in biomedical industry. The achievements of novel bioreactors including the applications of novel bioreactor technology and process analytical technology are also summarized. Finally, we discussed the development status and problems of bioreactor industry in China and pointed out that increasing the product quality rather than production is the goal of bioreactor development. This review also expounded the key role of modern bioreactor technology and the "Quality by Design" principles of, as well as the developmenet status and trend of bioreactor technology.
    Chemical processes and equipments
    Current research and technical progress in membrane distillation process intensification and optimization
    GUO Zhi, ZHANG Xinmiao, ZHANG Chenlin, LUAN Jinyi
    2016, 35(04):  981-987.  doi:10.16085/j.issn.1000-6613.2016.04.002
    Abstract ( 667 )   PDF (9549KB) ( 566 )  
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    Membrane distillation(MD) is an emerging membrane separation process, and has started to receive more research concern recently due to its several attractive and unique features, such as high salt rejection rate, being capable of treating high concentration feed etc. MD can be applied for different applications, including seawater desalination, wastewater treatment and various solutions concentrating process. However, the industrialization of MD is limited to some extent because of its relatively higher energy consumption and process cost. The current status of MD intensification and optimization research has been highlighted in this paper. It has reviewed the research progress of membrane material and fabrication methods, optimization of MD operating parameters, membrane module improvement and auxiliary equipment integration, utilization of solar and low-grade thermal energy, recycling the evaporation/condensation latent heat as well as hybrid MD system with other separation process. Meanwhile, the application of MD in the treatment of industrial high concentration saline wastewater was proposed and analyzed. Moreover, the research directions of MD process intensification and optimization were discussed and summarized, which would provide insightful guidelines for the further development of MD technique.
    Research progress of hydrocracking reaction kinetic model
    LI Zhonghua,XIAO Wu,RUAN Xuehua, HE Gaohong
    2016, 35(04):  988-994.  doi:10.16085/j.issn.1000-6613.2016.04.003
    Abstract ( 671 )   PDF (2363KB) ( 510 )  
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    Hydrocracking is a key technology in the refining and petrochemical industry. With the help of reaction kinetics modeling and simulation techniques to understand hydrocracking mechanisms and to guide production, optimize plant operation can bring significant economic benefits could be achieved. This paper focuses on the use of lump method to study the relevant researches on hydrocracking reaction kinetics, including the kinetics models based on lumped by production method classification, discrete lumped and continuous lumped, describes the modeling method and development situation of these three kinds of lumped models, and presents the advantages and disadvantages of corresponding reaction networks. Comparison and analysis of the lumped models will provide a reference for modeling of hydrocracking. The continuous lumped model can take the properties of mixture and reaction pathways as well as changes of cutting schemes into consideration, then realize simulation of the complicated system hydrocracking reactor, and accurately predict distribution and properties of products. Meanwhile, further research direction of hydrocracking reaction kinetics modeling is also pointed out. Combining lump modeling and molecular modeling and developing a comprehensive mixed kinetic model will be a meaningful and challenging work in hydrocracking reactor simulation.
    Discussion on identifying energy,water and capacity expansion bottlenecks for refineries
    LIU Fuyu, FENG Xiao
    2016, 35(04):  995-999.  doi:10.16085/j.issn.1000-6613.2016.04.004
    Abstract ( 587 )   PDF (338KB) ( 341 )  
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    Refineries and chemical plants consume great amounts of energy and water. With increasingly stringent national requirements for energy conservation and emission reduction, these enterptises face more and more pressure. Process system integration and optimization technology dealing with an enterprise as a whole, can maximize energy and water saving effects. As an organic whole, a process system necessarily includes some unit processes that form the bottleneck of energy or/and water conservation, whose performance constrains the whole system's overall performance. Identificating such bottleneck, and studying the corresponding solution strategy, will get twice the result with half the effort of energy and water conservation. Based on energy system and water network optimization techniques and methods, this paper analyzes research progress of bottleneck identification on energy conservation, water conservation and plant retrofit for refineries and chemical plants. Current researches focus on bottleneck identification of single-function networks, and further research should pay attention to multi-function networks bottleneck identification.
    Development and application of integrated management system of smart factory
    ZHANG Zhiqiang, HU Shanying, HU Xueyao, GUAN Yanling, JIA Shengju
    2016, 35(04):  1000-1006.  doi:10.16085/j.issn.1000-6613.2016.04.005
    Abstract ( 675 )   PDF (23768KB) ( 238 )  
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    A reasonable theory and operation mode of smart factories have not been established in China. How to integrate the information resources efficiently, intuitively and rapidly, so as to support intelligent decision-making is the main problem that managers of the enterprises are facing. This paper proceeds from virtual reality which is the key technique of smart factory establishment, analyzes its modeling difficulties and problems in different kinds of plants in chemical industry. The authors use methods of three-dimensional geographic information modeling, laser point cloud scanning, and 360 degree panoramic image technique, combine with visual programming design technology, design and develop an integrated management system of smart factory. The system includes functions of interactive browsing, visual information query statistics, real-time security monitoring and forecasting, real-time environmental monitoring, real-time monitoring of production process and equipment, underground pipeline network management and safety protection, etc. It has achieved good application result in an enterprise, and provides a new way to solve the problem how to build a smart factory.
    Advances in the research development of isobutane/butene solid acid-catalyzed alkylation kinetics
    LIU Xiaoyu, ZHOU Xiang, GUO Jinbiao, WANG Xinlei, FU Weng
    2016, 35(04):  1007-1011.  doi:10.16085/j.issn.1000-6613.2016.04.006
    Abstract ( 814 )   PDF (2196KB) ( 363 )  
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    Kinetic analysis for understanding the reaction mechanism and hydrocarbon transformations rules has both theoretical and practical significance. The typical development and main research methods at different scales for alkylation kinetics are reviewed in this paper. Recommendations for improving the catalyst are made. The molecular-based kinetic modeling could provide detailed and explicit descriptions of the intrinsic kinetic properties, which reflect the relationship between the kinetic parameters and the feedstock, reaction conditions and catalyst. Mechanistic kinetic modeling could show important theoretical support for the optimization of reactor configuration, technological process and catalysts research.
    Solubility equilibrium of SO2 in the decalcified seawater
    XIE Yinghui, CAO Hainan, ZHAO Yingying, YUAN Junsheng
    2016, 35(04):  1012-1016.  doi:10.16085/j.issn.1000-6613.2016.04.007
    Abstract ( 712 )   PDF (4021KB) ( 839 )  
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    Compared with normal seawater, the content of HCO3- in the seawater of calcium removed using CO2 is higher. Because HCO3- can react with hydrogen sulfite produced by sulfur dioxide dissolving in water, which in return helps increase the solubility of sulfur dioxide. Therefore, the effect of the amount of HCO3- and Ca2+ on the solubility of sulfur dioxide in seawater was studied at temperatures of 34.0—63.9℃ with N2 as inert carrier gas and under 1atm. The results showed that the solubility of SO2 in standard seawater significantly reduced linearly with increasing temperature. The increase of HCO3- ion concentration in demineralized seawater will enhance the solubility of SO2 in water. But there is no significant effect of the reduction of Ca2+ ion concentration on the SO2 solubility within the studied scope. It can be concluded that sulfur dioxide shows a better dissolution performance in the seawater decalcified by CO2 than in the standard seawater, and this study provides a theoretical support to the coupling of flue gas desulfurization and seawater decalcification using CO2.
    Calculation of the gas flow rate through breather valve based on the method of peak mass conversation (PMC)
    KANG Yong
    2016, 35(04):  1017-1021.  doi:10.16085/j.issn.1000-6613.2016.04.008
    Abstract ( 845 )   PDF (1354KB) ( 444 )  
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    It is one of the requirements to ensure an oil storage tank equipped with breather valves for limiting its vented oil-gas capacity and keeping it in safety. As the variations of physical parameters caused with the time by surroundings of the oil storage tank, the uncertainty of the design of breather valves is increased. There are many physical parameters affecting the gas flow rate through valves. Temperature change is a main factor. Based on temperature variations, a new method, peak mass conversation(PMC), was presented to calculate the gas flow rate through breather valve. The method is referred to the mass change process of both gas phase and liquid phase as an independent mass conservation, taken the gas phase component of the conservation as a research object, and determined its peak gas flow rate under the saturated vapor pressure as the gas flow rate through breathing valve. By applying the principle of mass conservation, the formula for calculating gas flow rate through breather valve was obtained. Compared to the common methods, the PMC is helpful to get actual values as well as improves the accuracy of breather valve design and selection.
    Preliminary studies on the effective power consumption of rotating zigzag bed
    WANG Jianfeng, WANG Guangquan, CAO Weiwei, JI Jianbing
    2016, 35(04):  1022-1026.  doi:10.16085/j.issn.1000-6613.2016.04.009
    Abstract ( 631 )   PDF (4388KB) ( 352 )  
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    Rotating zigzag bed(RZB) is a novel kind of HIGEE equipment with concentric rings. Motor power consumption is an important factor to be considered when researchers design RZB. In this paper, experimental studies on the effective power consumption of RZB were preliminarily carried out. A new calculation method was proposed, which provided basis for studies on power consumption of rotating equipments and industrial applications of RZB. The effective power consumption of RZB could be divided into two parts:power consumption to disperse liquid and to accelerate liquid. The calculation model of the effective power consumption of RZB was achieved by theoretical analysis. Using water as test system, the effective power consumption was experimentally measured. According to the experimental data, the effective power consumption approximately linearly increased with liquid flowrate when rotating speed was constant. The higher rotating speed was, the more rapidly effective power consumption increased. Based on the experimental data, the model of effective power consumption with liquid flowrate and rotating speed for rotor with single concentric ring could be achieved. The relative deviation between the experimental data and the calculated values was within 20%. The calculated effective power consumption of RZB with four concentric rings is about 20% higher than the measured values, which is of certain significance for scale-up of RZB.
    Efficiency of working fluid pump in a small-scale organic Rankine cycle system
    YE Jiaqi, ZHAO Li, DENG Shuai, WANG Xiaodong, SU Wen
    2016, 35(04):  1027-1032.  doi:10.16085/j.issn.1000-6613.2016.04.010
    Abstract ( 757 )   PDF (3258KB) ( 566 )  
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    The isentropic efficiency of the working fluid pump in a small-scale power system of organic Rankine cycle (ORC) was experimentally studied under designed variable conditions. The selection and principle of the working fluid pump were focused. A small-scale power system of ORC using R245fa as working fluid was established. The volume type working fluid pump was chosen. The pressure difference of pump inlet and outlet pressure and the mass flowrate of system were controlled respectively. The experimental results showed that, the ORC system working fluid pump's isentropic efficiency was about 15% to 47% under the condition that evaporation temperature is 75℃ and condensing temperature is 11℃. The pressure difference between the inlet and outlet of the working fluid pump increased with the increase of mass flowrate of system. The isentropic efficiency increased, and largerly affected by the mass flowrate. The experiments confirmed that the estimation efficiency of the working fluid pump in the ORC system is much lower than that of the previously value used in simulation, calculation and industrial applications. The experimental working fluid pump isentropic efficiency of the average value of 30% is more appropriate. From isentropic aspect, the ratio of pump power for expander to output power should be 8%. For the actual process, the ratio should be greater than 12% by considering the efficiency of the pump and the motor.
    Multi-objective modeling and optimization for the water supply network of a coking plant
    HAN Geng, CAO Cuiwen, GU Xingsheng
    2016, 35(04):  1033-1041.  doi:10.16085/j.issn.1000-6613.2016.04.011
    Abstract ( 615 )   PDF (10467KB) ( 192 )  
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    In this paper, the water supply network system of a real-world cooking plant was deeply analyzed. Under the balance between water supply and demand, a bi-objective mixed-integer nonlinear programming(MINLP) model was built. Minimizing the fresh water supply and the total cost of fresh water, recycle water and desalting water were the two objectives. The Pareto based multi-objective cultural differential evolution(MO-CDE) algorithm of reference was selected to solve this model. The computing results showed that the bi-objective optimal results were better than current operational parameters in reducing the fresh water supply and the cost of fresh water, recycle water and desalting water.
    Heat transfer enhancement on shells of double-pipe exchanger with double helix fins
    LI Yaxia, ZHANG Teng, ZHANG Chunmei, ZHANG Li, WU Jianhua
    2016, 35(04):  1042-1046.  doi:10.16085/j.issn.1000-6613.2016.04.012
    Abstract ( 689 )   PDF (4902KB) ( 277 )  
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    Experimental and numerical methods were adopted to study the heat transfer enhancement effect for double-pipe exchangers by installing high and low double strand helix fins on the outer wall of inner tube. The double-pipe heat exchanger with single high helical fin was treated as referenced structure. The curvature ratios were set to 0.44, 0.321 and 0.131 and the Reynolds number was in the range of 4000 to 20000. The impact of the ratio of low to high helical fin heights on the average Nusselt number of shell wall Num and flow resistance coefficient f were studied. The comprehensive heat transfer performances of heat exchanger were examined at the same pump power condition. The study on heat exchanger with ε=0.44 showed that enhanced heat transfer effect was distinct when l/W value is greater than 1/2. The condition of l/W=3/4 is an optimal plan. For this case, the Num of heat exchanger with double helical fins was improved by 10.8 percent on average compared to that of single high fins. PEC values are in the range of 1.044 to 1.204 within the researched scope. The study on heat exchangers with different ε values showed that PEC values are raised with the increases of curvature ratio ε at the same l/W values, which indicates that low and high double helical fins are more suitable to double-pipe exchangers with larger curvature ratio.
    Lagrange multiplier method combined with structure evolution strategy for heat exchanger network synthesis
    ZHANG Chunwei, CUI Guomin, CHEN Shang, TAO Jianan
    2016, 35(04):  1047-1055.  doi:10.16085/j.issn.1000-6613.2016.04.013
    Abstract ( 587 )   PDF (3094KB) ( 350 )  
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    In allusion to the deficiency of penalty functions for constrained problems, a Lagrange multiplier method was adopted to optimize the heat exchanger network. To solve the Lagrange function equations, the steepest-descent method and the Powell method solving strategy according to the deterministic approach were proposed. The minimum value judgment mechanism ensures that the Lagrange function equation solution equals the minimum objective function value of the original network. According to the actual working conditions, a structure evolution strategy combined with a Lagrange multiplier method was proposed to reach the aim of global optimization. The validity and accuracy of these two methods, as well as the universality of the structure evolution strategy were verified by two benchmark problems. Compared with literature results, the proposed approaches have both strong local and global search abilities to find better heat exchanger network structures, which is conducive to cost saving in industrial production.
    Design and analysis of marine distillation fresh water generator
    FENG Dongdong, YUE Pengfei, ZHANG Fengming, YOU Xianren, CHEN Shunquan, KUANG Wanjun
    2016, 35(04):  1056-1061.  doi:10.16085/j.issn.1000-6613.2016.04.014
    Abstract ( 834 )   PDF (7469KB) ( 258 )  
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    Fresh water generator is one of the important marine auxiliaries. It uses steam or cooling liquid waste heat from internal combustion engine cylinder as the driving heat source and provides fresh water for the ship. It is a trend that tube and shell heat exchanger was replaced by the plate type heat exchanger in the field of marine distillation fresh water generator while the design of relevant products is scarce in literatures in China. Operating conditions were selected through study of thermodynamic calculation and heat transfer calculation of distiller. The structure of ejector device was improved to improve performance. These are all for the sake of the overall process design for the fresh water generator from the perspective of thermodynamics and fluid mechanics. The driving force of the fresh water generator is internal combustion engine cooling fluid waste heat. Theoretical yield of fresh water was calculated with analysis and research the design key points of the generator at operation features. The experimental results showed that the fresh water quality and the operating characteristics of the fresh water generator meet the design requirements. It can provide reference for plate type fresh water generator manufacture and research.
    Distillation parameters optimization based on heat exchanger network integration of xylene separation process
    ZHANG Di, LIU Guilian
    2016, 35(04):  1062-1067.  doi:10.16085/j.issn.1000-6613.2016.04.015
    Abstract ( 641 )   PDF (3031KB) ( 278 )  
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    Distillation is an important energy-consuming device of chemical process. Temperature variation of its products affects integration of heat exchange network. For the xylene separation process, the effect of distillation column's operating pressure was studied in this work. When the pressure of column DA604 increased to 170kPa and 230kPa, respectively, the composite curve was constructed and used to analyze variation of the pinch and minimum utility consumption. When the pressure increased from 110kPa to 170kPa, the pinch kept unchanged; heating utility decreased by 1948.5kW, while cooling utility increased by 1765.0kW. When the pressure increased from 110kPa to 230kPa, coolinging utility increased by 4964.1kW, while heating utility decreased by 8172.4kW. Namely, the heat demands can be saved and recovered heat by 6223.9kW. The results were the same with those calculated by the pinch analysis method. So when increasing the pressure of a distillation column whose top and bottom products are both sources, heating utility will decrease while cooling utility will increase. It is beneficial for energy saving of the system.
    Experiment on heat dispersion of finned lithium battery thermal management system
    GAO Ming, ZHANG Ning, WANG Shixue, ZHANG Jingjing, JIN Pengchao
    2016, 35(04):  1068-1073.  doi:10.16085/j.issn.1000-6613.2016.04.016
    Abstract ( 715 )   PDF (7057KB) ( 315 )  
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    Lithium-ion batteries continuously generate heat during work, So, when used as electric vehicle power supply, the battery pack may be quite hot and the temperature differences among monomers may be very large without effective thermal management measures, which will deteriorate its performance and lifespan. Generally uses various techniques such as forced air cooling, liquid circulation cooling, phase change material cooling and heat pipe cooling, have been applied in Battery thermal management system(BTMs) but with the shortcomings of complicated structure and high cost. In this work, pure copper fins were proposed for BTMs and experimental research was conducted. By changing the discharge rate and thickness of fins, the thermal characteristics of the battery pack under different working conditions is studied. The results showed that under the condition of natural convection, adding fin could significantly keep the temperature of battery pack from overheating, and improve the temperature distribution inside the battery pack. Thicker fins can meet the temperature requirements of higher discharge rate and greater discharge depth.
    Energy processes and technology
    Composition of acidic compounds in petroleum fraction
    XIAO Lixia, LÜ Ya
    2016, 35(04):  1074-1080.  doi:10.16085/j.issn.1000-6613.2016.04.017
    Abstract ( 614 )   PDF (13712KB) ( 195 )  
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    The acidic compounds in the feedstock of a refinery(vacuum cut 3) made devices corroded seriously, so the composition and distribution of the acidic compounds were analyzed by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectroscopy (negative-ion ESI FT-ICR MS). The acid fraction was extracted by alkaline-ethanol extraction prior to analysis, and compared with the industrial-grade naphthenic acids. The specialty of the acidic compounds in the feedstock of the refinery was explained from the molecular level. Negative-ion ESI FT-ICR MS revealed that the O2 class of the extracted acid fraction in the feedstock was dominated by acyclic carboxylic acids (belong to Z=0 family), and those had higher relative abundance of some compounds belonged to Z=-8 and-10 families of the O2 class, which leads the carbon number distribution curve has two peaks. The relative abundance of O1 class was much higher than that of other classes except for O2 class. The O1 class was dominated by alkylphenols. The special composition and distribution of acidic compounds has an important guiding significance to study the mechanism of corrosion and seek treatments for equipment corrosion.
    Extractive denitrification of coal tar diesel fraction using phosphate-based alkylimidazolium ionic liquids
    SU Xiaolin, SONG Jun, YANG Jingyi, XU Xinru
    2016, 35(04):  1081-1086.  doi:10.16085/j.issn.1000-6613.2016.04.018
    Abstract ( 706 )   PDF (5177KB) ( 331 )  
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    Two series phosphate-based alkylimidazolium ionic liquids (ILs), dialkyl and dihydrogen phosphate alkylimidazolium ILs were prepared and used to remove nitrogen compounds in the coal tar diesel fraction by extraction. The denitrification effect were studied under different conditions. The results indicate that dihydrogen phosphate alkylimidazolium ILs have a higher denitrification rate for both basic and non-basic nitrogen compounds than dialkyl phosphate alkylimidazolium ILs due to the complexation. The best denitrification rate can reach 92.3% using 1-butyl-3-methylimidazolium dihydrogen phosphate ([BMim]H2PO4) ILs as the extraction agent under the optimum conditions, with which the mass ratio of ILs to oil is 0.2, temperature is 40℃, reaction and stratification time are both 30min. [BMim]H2PO4 ILs performed stably in nitrogen removal of coal tar diesel fraction, and the denitrification rate remained almost no change even after five times reuse.
    Industrial catalysis
    Progress on the rhodium-based catalysts for the synthesis of higher alcohol
    HAN Tong, ZHAO Lin, YUE Yizhi, LIU Yuan
    2016, 35(04):  1087-1093.  doi:10.16085/j.issn.1000-6613.2016.04.019
    Abstract ( 622 )   PDF (2479KB) ( 583 )  
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    Literature reviews of Rh-based catalysts for higher alcohol synthesis has been made in this article. Mainly four topics of reaction mechanism, active sites, additives and carriers are discussed. We compared reports from different researchers, and found that controversies of reaction mechanism and active sites are still existed. Further researches are still needed. Though rhodium based catalysts exhibit high alcohol selectivity and good stability, its low reaction activities and high price still limit the large scale application, so efficient catalyst with high industrial applications values are still needed to study.
    Research advance review on supported Mn-based catalysts at low-temperature selective catalytic reduction of NOx with NH3
    YANG Yongli, XU Dongyao, CHAO Chunyan, GAO Ming
    2016, 35(04):  1094-1100.  doi:10.16085/j.issn.1000-6613.2016.04.020
    Abstract ( 812 )   PDF (2168KB) ( 1121 )  
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    MnOx has become a catalyst research hot spot low-temperature selective catalytic reduction of NOx with NH3, because of its good catalytic activity. Supported Mn-based catalysts could greatly overcome the problems such as poor N2 selectivity at low temperature and easily being poisoned, et al, and therefore have good prospects for industrial applications. This paper presents the research progress of Mn-based low-temperature De-NOx catalysts, from their active ingredients, carriers, mechanism, kinetics, and abilities of anti-H2O and SO2. The latest achievements on the preparation method and denitrification activity of artificial and natural carrier based such as the metal oxide, molecular sieve, and carbon based supported MnOx were explained in detail. It also summarizes the progress of the catalytic mechanism and kinetics of Mn-based low-temperature denitration catalysts, and analyzes the poisoning mechanism of H2O and SO2. It is pointed out that improving the anti-poisoning performance and regeneration are the focus of future research.
    Advances in research on V2O5/TiO2 catalysts for the gas-phase oxidation of 3-picoline to nicotinic acid
    HU Xiaobo, YUAN Weijie, ZHU Qiulian, CHEN Yinfei, LU Hanfeng
    2016, 35(04):  1101-1106.  doi:10.16085/j.issn.1000-6613.2016.04.021
    Abstract ( 627 )   PDF (1212KB) ( 265 )  
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    Nicotinic acid has been widely used in different fields as the important chemical and pharmaceutical intermediate.Compared with other traditional technology for production of nicotinic acid, one-step gas phase oxidation of 3-picoline has remarkable advantages of low cost, easy product separation, high product quality and few pollution.The oxidative reaction of 3-picoline on V2O5/TiO2 catalysts had rather high activity.Thus the paper reviews the recent research progress of oxidation 3-picoline to nicotinic acid on V2O5/TiO2 catalysts. It analyzed the surface structures of the catalysts by carrier and the influence factors from the preparation methods, loading content of V2O5, calcination temperature and time and doping additives. It also discussed the effects of interactions among various catalytic species, and the mechanism of the catalytic reaction. Defects of low reaction rate and selectivity, narrow temperature window and the heat of exothermic reaction were also explained. Finally, the application perspective and future development in the field of V2O5/TiO2 catalysts and the reactor design were explored.
    Denitration performance of supported Mn-Fe/γ-Al2O3 catalyst at low temperature
    CHEN Huanzhang, LI Hong, LI Hua
    2016, 35(04):  1107-1112.  doi:10.16085/j.issn.1000-6613.2016.04.022
    Abstract ( 704 )   PDF (42150KB) ( 259 )  
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    Low-temperature denitration catalyst Mn-Fe/γ-Al2O3 was prepared by the co-precipitation method. The performance of the catalysts for SCR reaction was evaluated with ammonia gas as the reductant in a fixed bed catalyst reactor. The effects of loading, active component ratio, calcination temperature, space velocity, oxygen content and mole ratio of NH3/NO on the catalysts' performance at low temperature were examined. The catalysts were characterized by XRD and BET techniques. The result showed that NO conversion over the catalyst could be above 96% at 200℃ when the conditions of the metal loading of 20%, molar ratio of Mn/Fe 4:1, space velocity of 16000h-1, oxygen content of 4%, and mole NH3/NO ratio of 1.2, were adopted.
    Enhanced catalytic properties of MOF-199 with water treatment in the direct hydroxylation of benzene
    LIU Yanfeng, ZHANG Tianyong, WU Wubin, LI Bin, ZHOU Zheng, ZHOU Haohao
    2016, 35(04):  1113-1120.  doi:10.16085/j.issn.1000-6613.2016.04.023
    Abstract ( 735 )   PDF (5874KB) ( 521 )  
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    Cu(OAc)2·H2O was treated with benzenetricarboxylic acid under stirring to form metal-organic framework MOF-199, which was then characterized by XRD, IR and BET. The obtained MOF-199 was treated with water and then applied for the hydroxylation of benzene as catalyst. The effect factors of MOF-199 amount, reaction temperature, reaction time, H2O2 amount on the yield and the selectivity of benzene oxygenates were investigated. Results indicated suitable conditions for the preparation of benzene oxygenates, were that the water-treated MOF-199 (140mg, 0.23mmol), acetonitrile (4mL), benzene (1.1mL) and H2O2 (3.3mL) were mixed together, and then reacted for 30min at 60℃ in a water bath. The corresponding oxygenates had a yield of 23.3%, the selectivity to phenol of 53.1%, and the turnover frequency(TOF) was 25.0h-1. Pretreatment of MOF-199 catalyst with water significantly accelerated the catalytic oxidation of benzene to the corresponding oxygenates and preserved the metal-organic framework of MOF-199 due to the formation of a new reaction mode.
    Synthesis and photocatalytic activity of Eu-doped BiVO4 nanosheets by hydrothermal method
    WANG Zhixin, HUANG Shaobin, FEI Zhibin, JIAN Zicong
    2016, 35(04):  1121-1125.  doi:10.16085/j.issn.1000-6613.2016.04.024
    Abstract ( 693 )   PDF (8070KB) ( 283 )  
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    Eu-doped BiVO4 photocatalysts were synthesized by hydrothermal method using PEG-200 as the template. The material were characterized by XRD, SEM, UV-vis DRS and BET. The photocatalytic degradation rate of methyl blue was used to investigate the influence of the dopants for the photocatalytic activity of BiVO4. The results revealed that the dopants had a significant effect on the transition of crystal phase, prevention of the crystal growth and the increase of BET. Some Bi3+ in the BiVO4 crystal lattice were substituted by Eu3+ leading to a crystal distortion, which was beneficial for the enhancement of photocatalytic activity. For 50% Eu-doped BiVO4 nanosheets, it performed with the best photocatalytic activity. The photodegradation rate of MB was 90% after 120min visible light irradiation, which was much higher than that of pure BiVO4.
    Material science and technology
    Progress in preparation and application of sodium alginate antibacterial materials
    HU Yongli, ZHANG Shuping
    2016, 35(04):  1126-1131.  doi:10.16085/j.issn.1000-6613.2016.04.025
    Abstract ( 783 )   PDF (397KB) ( 785 )  
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    This review starts with a brief introduction of the principles and methods of electrospinning technique as well as their applications in the preparation of composite nano-biomaterials. The use of electrospinning technique can add new features to materials by combining variety of substances into one single nanofiber, which has acquired extensive attention in the field of the synthesis of multifunctional composite materials and showed a great potential. Sodium alginate nanomaterials with excellent physiochemical properties, functional characteristics, biocompatibility and specific nano-size effects can be fabricated into antibacterial composite films using silver nanoparticles as the antibacterial agent based on elecrospinning technique. These films play an important role in food packaging, wound dressing, drug delivery and tissue engineering scaffold. Additionally, a couple of problems such as how to optimize the modifier of sodium alginate, how to choose antibacterial agent etc. are introduced and application perspective of electrospinning technique on the preparation of sodium alginate antibacterial composite films is discussed.
    Preparation and characterization of Zn2+-bi-templates imprinted polymers for the simultaneous extraction of ferulic acid and caffeic acid in Rhizoma Cimicifugae
    WANG Susu, ZHANG Yue, LI Hui
    2016, 35(04):  1132-1139.  doi:10.16085/j.issn.1000-6613.2016.04.026
    Abstract ( 575 )   PDF (9458KB) ( 231 )  
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    A group of bi-templates imprinted polymers (MIPs) was synthesized using Zn2+-ferulic acid-caffeic acid complex as the template. The preparation conditions were optimized. Structural characterizations were performed using FTIR and SEM and the adsorption capacity was tested. Also, the applicability of this MIP in the solid phase extraction was explored after the washing and elution conditions were optimized. Results indicated that when the molar ratio of Zn2+-two templates (the molar ratio of ferulic acid to caffeic acid was 2:3)-functional monomer-cross linker was 1:1:3:30 in the pre-polymerization mixture, the obtained imprinted polymer possessed the highest adsorption capacity toward two templates, with a value of 51.12mg/g for ferulic acid and 70.26mg/g for caffeic acid. The adsorption equilibrium can be reached within 3h. The optimized conditions for this MIPs phase extraction were 1.00mL H2O, 1.00mL methanol-H2O mixture (3/7, volume ratio) and 1.00 mL methanol-H2O-acetonitrile mixture(4/4/2, volume ratio) for the washing procedure and 2.00 mL methanol for the elution one. This MIP revealed selective enrichment capability toward ferulic acid and caffeic acid in the crude extract of Rhizoma Cimicifugae, with recovery rates of 92.67% and 95.42% respectively under the optimized conditions. The product contains less impurities than that obtained by silica solid phase extraction.
    Thermal stability of high power lithium-ion battery electrolytes
    ZHANG Xu, WANG Zhi, WANG Xu, CHEN Jian, GENG Su
    2016, 35(04):  1140-1143.  doi:10.16085/j.issn.1000-6613.2016.04.027
    Abstract ( 688 )   PDF (3021KB) ( 434 )  
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    The high power lithium-ion power battery is the key part of the electric powered aircraft. Whether the battery can keep normal working condition will directly determine the safety of the driver, passenger and aircraft. Therefore, the study on the safety of the high power lithium-ion power battery is very important for the spread of electric aircraft and other clean energy projects. The thermal stability of high power lithium-ion battery electrolytes is investigated in the current work. The TDB-6A flash point tester is used to determine closed cup flash point of six kinds of electrolytes. And then, the thermal runaway reactions of these electrolytes are studied using ARSST during the heating process. On the basis of these results, it can be obtained that the thermal stability of these electrolytes ranks as YH-51-7, YH-11-15, YH-61-7, YH-65-6, YH-51-6 and YH-51-8. This work is helpful for the safety investigation of high power lithium-ion batteries in light electric aircraft.
    Phenolic foam modified with polyurethane prepolymer
    WU Chongzhen, GAO Shuya, ZHANG Li
    2016, 35(04):  1144-1148.  doi:10.16085/j.issn.1000-6613.2016.04.028
    Abstract ( 630 )   PDF (2084KB) ( 367 )  
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    The toughening phenolic foam with low pulverization was prepared by adding polyurethane prepolymer which is terminated with isocyanate and without free isocyanate monomer, and by reducing the consumption of acidic curing agent in the foaming process. The effect of isocyanate content on the apparent density, compressive strength, water intake, flame retardant and heat conductivity of phenolic foam were also discussed. The results showed that the apparent density and compressive strength of the modified phenolic foam tended to increase with the content of polyurethane prepolymer and corresponding isocyanate group. Meanwhile, the resistance to pulverization is the best when the isocyanate content is 8.6%. However, the water absorption and heat conductivity of the modified polyurethane foam changed little with the increase of polyurethane prepolymer. The critical oxygen index was still more than 40 when the content of polyurethane was less than 6%.
    Effect of different preparation methods on the properties of magnesium hydroxide nanoparticles
    SHEN Hongyan, LIU Youzhi, MA Pengcheng, SUO Qi, LIU Xueli, PENG Yunpeng, ZHU Zhimin
    2016, 35(04):  1149-1153.  doi:10.16085/j.issn.1000-6613.2016.04.029
    Abstract ( 960 )   PDF (4398KB) ( 505 )  
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    Magnesium hydroxide nanoparticles were prepared via ordinal precipitation method, reverse precipitation method, double precipitation method and high-gravity precipitation method using magnesium chloride hexahydrate as raw material and sodium hydroxide as precipitant. The settling velocity was selected as the index to investigate the effects of different preparation methods on the settlement property of magnesium hydroxide slurry. The morphology, particle size and its distribution, and crystal phase of the samples were characterized by transmission electron microscope (TEM), laser particle size analyzer (LPSA), and X-ray diffractometer (XRD), respectively. The results showed that the settling velocity increased evidently via high-gravity precipitation method, which was 4.7 times, 12.4 times and 2.1 times of that by the ordinal precipitation method, reverse precipitation method and double precipitation method. It was also found that the samples prepared by high-gravity precipitation method were hexagonal flake-like shape with narrow particle size distribution, high purity and good dispersity.
    Synthesis of dual-core basic ionic liquids and its application for anion exchange membranes
    CHEN Lihao, WANG Lulu, WANG Jilin, FENG Ruijiang, LÜ Zhenbo
    2016, 35(04):  1154-1161.  doi:10.16085/j.issn.1000-6613.2016.04.030
    Abstract ( 1047 )   PDF (9633KB) ( 394 )  
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    A new basic dicationic morpholine ionic liquid (IL) was synthesized with Bromodecane, morphline and 1, 4-dibromobutane via a two-step procedure. The structure of new IL was characterized by FTIR, 1HNMR spectra and the thermal stability was analyzed by TGA. The alkalinity and solubility of the dicationic IL were also measured. Meanwhile, a series of anion exchange membrane (QCS/[Nbmd]OH) were prepared by the casting method with quaternized chitosan (QCS) as raw material and the alkaline ionic liquids ([Nbmd]OH) as dopants. The structure, thermal stability and morphology of the composite membrane prepared in this paper were characterized by FTIR, TGA and SEM. Then the influence of dopping amount of ionic liquid on the water content, mechanical properties and conductivity of the composite membrane was also investigated. It was showed that the water content, ion exchange capacity, anionic conductivity increased and tensile strength, elongation at break decreased with the increases of amount ionic liquids ([Nbmd]OH) in the membranes. The anionic conductivity, tensile strength, ion exchange capacity, water content and wet-swelling rate could respectively reach 1.17 ×10-2 S/cm, 11.8 MPa, 1.26 mmol/g, 320% and 236% at 70℃ and the mass fraction of ionic liquids of 30%.
    Preparation of roxithromycin molecularly imprinted layer-coated silica and its selective adsorption properties
    TANG Zhimin, MA Xinbin
    2016, 35(04):  1162-1166.  doi:10.16085/j.issn.1000-6613.2016.04.031
    Abstract ( 639 )   PDF (6979KB) ( 221 )  
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    Roxithromycin molecularly imprinted silica was prepared by using AMPS as the silica surface modifier, methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the crosslinker, and roxithromycin as the template molecule. Its structure was characterized by infrared spectroscopy, scanning electron microscope and particle size analysis. The adsorption properties of ROX-MIP-PMAA/SiO2 on roxithromycin were studied by static binding test and dynamic binding test, and its selective adsorption properties was investigated by selective binding test with erythromycin as the competing substrate. Results showed that the roxithromycin adsorption capacity of ROX-MIP-PMAA/SiO2 was better than that of NIP-PMAA/SiO2. The separation factor of roxithromycin and erythromycin for ROX-MIP-PMAA/SiO2 was 1.21, showing that ROX-MIP-PMAA/SiO2 displayed high recognition ability to the template molecule.
    Biochemical and pharmaceutical engineering
    Research progress on fungicides during ethanol fermentation
    ZHANG Qiang
    2016, 35(04):  1167-1172.  doi:10.16085/j.issn.1000-6613.2016.04.032
    Abstract ( 681 )   PDF (1817KB) ( 412 )  
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    Ethanol fermentation is a complex microbial process. During the process, a significant number of bacteria will be brought in from raw materials, air, water, etc., which will reduce yield of ethanol and affect production of ethanol. Therefore, how to effectively control the bacteria infection is essential for the ethanol production. Research progress on fungicides during ethanol fermentation was reviewed in this paper. The source, contamination, testing methods of the common harmful bacteria during ethanol fermentation were introduced focusing on the application of bleaching powder, penicillin, "kejunling" and hops and plant extracts. Reducing the bacteria infection during ethanol fermentation, strengthening the study of bacteria resistance and finding safe and natural alternatives to fungicides are the keys to future research.
    Progress on effects of metal ions on lipid accumulation of oleaginous microorganism
    LI Tao, JI Xiaojun, WU Na, ZONG Jiajun, HUANG He, YU Yadong
    2016, 35(04):  1173-1179.  doi:10.16085/j.issn.1000-6613.2016.04.033
    Abstract ( 719 )   PDF (5728KB) ( 557 )  
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    Using oleaginous microorganism to produce lipid is meaningful for overcoming fossil-fuel shortage and improving human life quality. Metal ions can affect the growth morphology, intra-/extra-cellular osmotic pressure and the activity of the key enzyme during the oleaginous microorganism lipid accumulation. Therefore, metal ions are important regulators for oleaginous microorganism. In this review, we discussed the mechanism of oleaginous microorganism lipid accumulation and then explained which metal ions affected oleaginous microorganism and how. Finally, we gave some suggestions on the future studies in exploring the role of metal ions in oleaginous microorganism fermentation process. In order to develop feasible metal ion addition and control strategy for oleaginous microorganism, the following factors might need to be considered. First, we should find the key enzyme from various lipid synthesis pathway of oleaginous microorganism. Then we should fully consider the metal ion tolerance of the target oleaginous microorganism, the effects of different metal ion on the microorganism morphology and the activities of the key intracellular enzymes. Moreover, we should explore the competitive or collaborative relationship among different metal ions when these metal ions could all affect the active centers of the key enzymes.
    Increasing productivity of phosphatidyserine by repeated batch reaction
    FENG Juanjuan, ZHU Nannan, DENG Yangmin, HAN Xiaoling, ZHANG Xiaoli, ZHAO Binxia
    2016, 35(04):  1180-1183.  doi:10.16085/j.issn.1000-6613.2016.04.034
    Abstract ( 629 )   PDF (1204KB) ( 284 )  
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    The synthetic reaction of phosphatidyserine from soybean lecithin catalyzed by immobilized phospholipase D was carried out in oil-water two phase system, with PC and L-serine rich in oil and water phase, respectively. However, the by-product choline restrains the enzyme-catalyzed reaction rate and should be removed in time. In order to solve this problem, we adopted the repeated batch reaction. Increasing the substrate (PC) concentration decreased the yield of PS greatly. When various concentrations of choline chloride were added into the reaction mixture at low PC concentrations, there was a significant decrease in transphosphatidylation rate and the yield of PS. The using of repeated batch reaction was examined at high PC concentration to remove choline, the transphosphatidylation rate increased by 38%, and PS yield was 67%. The paper reported that the repeated batch operation is a novel technology for the synthesis of phosphlipid and increased the productivity of PS significantly. And the immobilized enzyme activity remained 58% after ten batches and nano-SiO2-immobilized-PLD was suitable for repeated batch reaction.
    Screening,identification of hydrogenogen and the research of its fermentation performance
    ZHANG Cunsheng, WANG Wenjuan, WANG Zhenbin, SHAO Shuping, MA Haile
    2016, 35(04):  1184-1189.  doi:10.16085/j.issn.1000-6613.2016.04.035
    Abstract ( 667 )   PDF (8411KB) ( 176 )  
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    In order to obtain high performance hydrogen-producing bacteria, two strains (H-1 and H-2) were screened from activated sludge which was pretreated by alkali. Biological identification showed that the two strains were of Enterobacter species. H-1 was Enterobacter cancerogeous HG6 2A species and H-2 had the closest relationship with Enterobacter homaechei83. Results showed that the best performance could be achieved from co-fermentation at the ratio of 1:1 (H-1:H-2). The corresponding fermentation time and hydrogen yield were 33h and 861mL/L, respectively. The defects of lower hydrogen yield by H-1 and longer fermentation time by H-2 were overcome by co-fermentation. The main volatile fatty acids (VFA) in the broth were acetate and butyrate, indicating that the fermentation of the two strains were both butyrate type. Due to the synergistic effect of the two strains, the accumulation rate of VFA reduced at the initial of fermentation. As a result, the stability of the system was enhanced.
    Fine chemicals
    Research progress in the synthesis of isophorone by acetone self-condensation
    LI Yunlong, LÜ Jiangang, JIN Zhaosheng
    2016, 35(04):  1190-1196.  doi:10.16085/j.issn.1000-6613.2016.04.036
    Abstract ( 854 )   PDF (890KB) ( 920 )  
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    In recent years, the acetone production keeps growing, resulting in excess production capacity in China. On the other hand, high value-added applications of acetone are relatively limited. The process of making acetone self-condensation into isophorone, and subsequently into isophorone diamine, isophorone diisocyanate, can greatly enhance the added value of acetone. The paper reviewed the production routes of isophorone by acetone self-condensation and the research progress of the catalysts. We emphasized to introduce the representative industrial production processes and catalysts, such as acetone liquid phase condensation with alkaline hydroxide as catalyst and acetone gas condensation with hydrotalcite as catalyst. Then, we further discussed the factors influencing the catalytic performance of Mg-Al solid base, and compared the advantages and disadvantages of the production routes of isophorone. Finally, the prospects of isophorone is forecasted.
    Synthesis of new AB monomers of amino modified PBO
    ZHAO Deming, WU Feng, CHEN Zhonghai, WU Chunxin, ZHANG Jianting, JIN Ningren
    2016, 35(04):  1197-1202.  doi:10.16085/j.issn.1000-6613.2016.04.037
    Abstract ( 630 )   PDF (2316KB) ( 292 )  
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    Using 4-methoxycarbonyl-2-nitro-benzoic acid (β-MNT) and 4-amino-6-nitroresorcinolhydrochloride (ANR·HCl) as the starting materials, we synthesized the intermediates 4-(5-nitro-6-hydroxybenzoxazole-2-yl)-3-nitro-methyl benzoate (3-NMNC), 4-(5-nitro-6-hydroxybenzoxazole-2-yl)-3-nitrobenzoate (3-NMNB), 4-(5-nitro-6-hydroxy benzoxazole-2-yl)-3-aminobenzoic acid (3-NNBA) and the final product 4-(5-amino-6-hydroxy benzoxazole-2-yl)-3-aminobenzoic acid (3-AABA) through a series of reaction, including acylchloride, N-acylation, cyclization, hydrolysis and catalytichydrogenation reduction reaction. The optimal cyclization, hydrolysis and catalytichydrogenation reduction conditions were obtained. The experimental results for the cyclization reaction showed that taking diethyleneglycol dimethyl ether as solvent, the polyphosphoric acid(PPA) as dehydrant and the content of P2O5 in PPA of 84%, w(3-NMNC):w(PPA)=1:9.5, the reaction temperature of 140℃ and the reaction time of 8h, we obtained the yield of 3-NMNB of 73.16% and its purity was 99.10% as determined by HPLC. The experimental results for the hydrolysis reaction showed that using ethanol and water as solvent, n(K2CO3):n(3-NMNB) = 1.8:1 and the reaction time of 2h, we got the yield of 3-NNBA of 74.19% and the purity was 98.59% as determined by HPLC. The experimental results for the hydrogenation reduction reaction showed that using methanol as solvent, w(10%Pd/C):w(3-NNBA)=1:20, pressure of hydrogen of 1.0 MPa, reaction temperature of 80℃, reaction time of 5h, we had the yield of 3-AABA of 65.08% based on 3-NNBA and the purity was 99.43% as determined by HPLC.
    Synthesis of citral from dehydrolinalool catalyzed by titanium isopropylate
    ZHAO Ningbo, ZHU Zhiqing
    2016, 35(04):  1203-1207.  doi:10.16085/j.issn.1000-6613.2016.04.038
    Abstract ( 696 )   PDF (3868KB) ( 347 )  
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    With titanium isopropylate as the primary catalyst and cuprous chloride as promoter, citral was synthesized from dehydrolinalool through Meyer-Schuster rearrangement in the presence of organic acid under nitrogen atmosphere. The optimized conditions were as follow:n(titanium isopropylate):n(cuprous chloride) was 4:1, the dosage of catalyst (titanium isopropylate + cuprous chloride) was 3.5% of dehydrolinalool, the amount of 4-methylbenzoic acid was 10% of dehydrolinalool, the reaction was operated at 110℃ for 3h. The conversion of dehydrolinalool was 98.8% and the yield of citral was 88.4%. Citral with purity of ≥97% was separated from reaction mixtures by steam distillation. The product was characterized by means of FTIR and the main impurities in the citral were also identified . The synthesis mechanism of citral from dehydrolinalool was discussed.
    Resource and environmental engineering
    Review of removal of heavy metal ions from wastewater with agricultural and forestry waste as adsorbent
    WEN Yonglin, LIU Pan, TANG Qi
    2016, 35(04):  1208-1215.  doi:10.16085/j.issn.1000-6613.2016.04.039
    Abstract ( 1013 )   PDF (1548KB) ( 640 )  
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    Industrial wastewater with heavy metals poses a serious threat to the environment, and bio-adsorption can effectively remove heavy metals. This paper firstly introduced current research status of common agricultural and forestry wastes and the modified reagents on absorption of heavy metals, then analyzed the influencing factors on bio-adsorption and the adsorption process optimization, followed by summarizing the mechanism of bio-adsorption and the desorption process and introducing the thermodynamic and kinetic models and related parameters. Finally, we pointed out the existing problems and development prospects of bio-adsorption. Agricultural and forestry waste has the advantages of wide range of sources, low cost and renewable. When used in wastewater treatment, it can achieve the full utilization of resources, so it has a good prospect in industrial application.
    Research progress of biological nitrogen removal by microbial fuel cell
    ZHAO Huimin, LI Xiaoling, ZHAO Jianqiang
    2016, 35(04):  1216-1222.  doi:10.16085/j.issn.1000-6613.2016.04.040
    Abstract ( 707 )   PDF (434KB) ( 567 )  
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    Microbial fuel cell (MFC) is a new technology for wastewater treatment while generating electricity simultaneously. Applying MFC to nitrogen removal makes the system denitrification MFC or simultaneous nitrification and denitrification (SND) MFC. This paper firstly gave an introduction on the development of biological denitrification in MFC system. Then we analyzed factors influencing MFC nitrogen removal efficiency. The analysis was mainly focused on the MFC configuration (space configuration, electrode materials, separation materials), the operation conditions (nitrogen components concentrations, HRT, dissolved oxygen, carbon source and C/N ratio, temperature, pH, external resistance), as well as the gene expression and diversity of denitrifying bacteria in systems. Finally, suggestions were proposed as following:developing high economic and efficient electrode materials with strong electron transfer ability and ammonia oxidation catalytic function, optimizing the operation conditions of the MFC denitrification systems and analyzing nitrogen removal mechanism, and screening efficient denitrification bacteria through the analysis of microbial community structure in MFC denitrification systems.
    Application progresses in the treatment of volatile organic compounds by adsorption on activated carbon
    XU Wei, LIU Junli, SUN Kang
    2016, 35(04):  1223-1229.  doi:10.16085/j.issn.1000-6613.2016.04.041
    Abstract ( 1030 )   PDF (430KB) ( 1479 )  
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    Volatile organic compounds(VOCs) is an important class of atmospheric pollutants, and the consequential environmental pollution problems have got wide attention. Activated carbon adsorption method is an effective method for controlling the pollution caused by VOCs. This paper embarks from the introduction of VOCs treatment technology, introducing the use of activated carbon adsorption method in the treatment of VOCs briefly. By summarizing the process technology and existing problems of treating VOCs by activated carbon, the thermal pressure swing adsorption, electric swing adsorption, with advantages of the high efficiency, energy conservation and environmental protection have good prospects for development in the treatment of VOCs. In addition, to provide a theoretical basis for improvement and development a special activated carbon for VOCs treatment, the influence of the surface chemical properties of activated carbon, the physical properties of the adsorbate, and the operating conditions of VOCs on activated carbon adsorption were analyzed. Based on the summarization of the existing research progresses, the development trend of the technology in removal of VOCs by activated carbon adsorption method was forecasted. The measures of improving process, coupling with other VOCs treatment technology, and developing varieties of activated carbons and diverse recovery equipment to accommodate the emissions of VOCs from different fields will be the research hotspots in the future.
    Electrochemical oxidation of phenol on AC/SnO2-Sb particle electrodes
    YANG Shengxiang, WANG Lizhang, WU Bo, ZHANG Bo, LI Zhenan
    2016, 35(04):  1230-1236.  doi:10.16085/j.issn.1000-6613.2016.04.042
    Abstract ( 605 )   PDF (11412KB) ( 186 )  
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    As SnO2-Sb solid solution have excellent catalytic activity, a kind of AC/SnO2-Sb particle electrodes was manufactured with thermal decomposition method. Nitrogen adsorption, scanning electron microscopy(SEM), X-ray diffraction(XRD) and electrochemical test were used to analyze the surface area, porosity, phase composition, the crystal structure and electrocatalytic activity of modified activated carbon(AC). The results showed that SnO2-Sb as continuous solid solution reduced quantity of mesoporous structures but not damaged high porosity of AC that is beneficial to the electrocatalysis. In addition, these metal oxide coatings widely distributed in the channel of AC, which could improve not only electrical catalytic activity to ·OH but also the direct oxidation activity on the surface of the electrode. Meanwhile cyclic voltammetry curve of AC/SnO2-Sb showed an obvious oxidation peak at 1.10V, which indicated direct oxidation of phenol can occur at the surface of AC/SnO2-Sb. Bulk electrolysis experiments with AC and AC/SnO2-Sb were conducted with simulated phenol wastewater. The results indicated the removal of COD and phenol with AC/SnO2-Sb(78.43% and 79.52%) were better than that of AC under 12.0mA/cm2 current density during 3h electrolysis. Moreover excellent electrochemical stability of AC/SnO2-Sb can be shown in 30 days continuous water treatment.
    Electrokinetic remediation of gold mine tailings polluted with copper
    GOU Kai, ZHANG Yingjie, SUN Xin, DONG Peng
    2016, 35(04):  1237-1241.  doi:10.16085/j.issn.1000-6613.2016.04.043
    Abstract ( 573 )   PDF (21347KB) ( 201 )  
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    In this paper, the gold mine tailings collected from Dali Bai autonomous, Heqing prefecture, Yunnan province, China were investigated by electrokinetic remediation. The effect of different anode electrode solution, permeable reactive barrier(PRB) materials and placement of the PRB on the removal rate of copper was studied. The morphological changes of copper in the electrokinetic remediation were also investigated. The percent of water soluble species, acid extractable fraction, Fe-Mn oxides species, organic matter species and residual species in total copper content were 0.7%, 5.8%, 40.9%, 9.7%, and 42.9% respectively. The results indicated that the removal rate of water soluble species, acid extractable fraction, Fe-Mn oxides species can reach 66.5%, 51.5% and 58.5% respectively when the anode electrode solution was 0.1mol/L citric acid solution and the PRB was coconut shell activated carbon and placed in 10cm away from the anode. Unfortunately there was almost no effect about organic matter species and residual species of copper. However, there were few reports about the research on electrokinetic remediation of mine tailings. This study can provide a reference for related research.
    Applied technology
    Dynamic characteristics of pressure-swing distillation for ethanol-chloroform separation
    XU Dongfang, HU Jiajing, WANG Lili, ZHU Zhaoyou, WANG Yinglong
    2016, 35(04):  1242-1249.  doi:10.16085/j.issn.1000-6613.2016.04.044
    Abstract ( 703 )   PDF (46864KB) ( 238 )  
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    The steady-state simulation of the pressure-swing distillation(PSD) for separating an azeotrope of ethanol-chloroform was studied based on the pressure-sensitive of the mixture. The process was optimized by minimizing the total annual cost(TAC) using Aspen Plus. The obtained purity of the products was more than 99.9%. The economy of different heat-integrated processes was investigated on the basis of steady-state simulation. The dynamic characteristics of different heat-integrated PSD for separating ethanol-chloroform binary azeotropic system were studied by Aspen Dynamics. Robust control strategies were built based on the characteristic of different heat-integrated PSD process. The results showed that the economy of the fully heat-integrated process was better than no and partially heat-integrated process and composition-temperature cascade control structure was suitable for no and partially heat-integrated PSD while pressure-compensated temperature control structure was useful for fully heat-integrated PSD. Although fully heat-integrated PSD has the optimal economic efficiency, partially heat-integrated PSD can achieve more robust control than fully heat-integrated PSD. The studies provide certain reference value for the separation of the lower alcohol binary azeotrope with heat-integrated PSD in industrial application.
    Chemical industry park
    Evaluation of VOCs emission control technologies in typical chemical industry park
    LI Jiayu, LIU Limin, HAN Jianhua, JI Hongbing
    2016, 35(04):  1250-1256.  doi:10.16085/j.issn.1000-6613.2016.04.045
    Abstract ( 828 )   PDF (2698KB) ( 726 )  
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    As volatile organic compounds(VOCs) emission problems of chemical industry park has attracted more and more attention, the choice of VOCs emission control technology in chemical industry park needs scientific, rational, objective and fair evaluation index system and assessment methods. An evaluation index system for VOCs emission control technology based on analytic hierarchy process was developed. For a typical chemical industry park, such as petrochemical industry, the industry distribution and VOCs emission characteristics were analyzed, and screening method of alternative technologies and determination of evaluation index weight were presented. An example to verify the method was also given. Evaluation index system of VOCs emission control technologies in a typical chemical industry park involving eight indexes could be applicable to enterprises in the typical chemical industrial park. The evaluation index system was comprehensive, qualitative and quantitative. A judgment matrix was constructed to calculate the eigenvalues of the matrix and vector features, consistency check was made, and then overall ranking of inter-level indicators was made to determine the weights of all index factors relative to the objective level. Finally, Huizhou Daya Bay Petrochemical Zone was taken as an example. The preferred selection was in the following order:Rotary zeolite adsorption-concentration and combustion > Granular carbon adsorption-concentration and combustion > Regenerative combustion. Rotary zeolite adsorption-concentration and combustion was selected as the best available technology due to its highest weight among those technologies.
    Product and market
    Chinese patent analysis of aromatic nylon's synthesis
    WAN Li, FENG Lianfang, GU Xueping
    2016, 35(04):  1257-1262.  doi:10.16085/j.issn.1000-6613.2016.04.046
    Abstract ( 592 )   PDF (3940KB) ( 856 )  
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    The Chinese patents in the field of aromatic polyamide's synthesis were reviewed. We summarized the existing patents based on the chemical structure, regional distribution and application affiliation, respectively. We also made a discussion of the patents based on the synthesis method. The reaction condition of polycondensation at low temperature is easy to achieve, but it needs organic solvent and therefore increases the cost. The temperature of interface polycondensation method is low, but it consumes large amount of solvent, and needs high reactive monomers. The raw materials of aqueous phase polycondensation is cheap, and has various temperature rise programming. It often uses batch operation and is widely applied in many aromatic nylon's synthesis. Direct melt polycondensation requires no solvent, and reacts in low pressure. But it can only be applied to monomers that is easy to melt. We conclude that the aromatic nylons with terephthalic acid as raw material have been studied extensively, while the aqueous phase polycondensation is the most suitable method for industrialization. It is expected to achieve some industrial applications in these areas in future.
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