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Table of Content
05 April 2017, Volume 36 Issue 04
    Development of the “Sixth Industry” and its support by chemical technology
    JIN Yong, LUO Zhibo, HU Shanyin, CHEN Dingjiang, ZHU Bing
    2017, 36(04):  1155-1164.  doi:10.16085/j.issn.1000-6613.2017.04.001
    Abstract ( 303 )   PDF (8056KB) ( 369 )  
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    At present,the traditional small-scale peasant economy has been unable to take on the responsibility of guaranteeing agricultural production and farmers' income increase. It is not conducive to food safety and environmental protection. The development of intensive agriculture is the general trend. The "Sixth Industry" is the development of modern agriculture as an excellent remedy for this situation. Among them,chemical products,such as chemical fertilizers,pesticides and agricultural plastic films,have made important contributions to the improvement of grain yields and the self-sufficiency of grain in China's agricultural development process. However,for the shortage of resources,changes in the environment and the development of agricultural modernization,it has put forward new demands of the agricultural chemical products and agrochemical services. This paper briefly reviews the development course of China's agricultural revolution,analyzes the connotation of the "Sixth Industry",and expounds the important supporting role of chemical engineering and agrochemical dustry to the development of agricultural revolution under the perspective of "Sixth Industry". In particular,the transformation of the agrochemical industry should focus on the development of new agricultural chemical products including new chemical fertilizers,new low-toxicity pesticides and high-performance degradable plastic film. The traditional form of fertilizer application is also need to reform,which can promote the integration of water and fertilizer integrated irrigation technology. In addition,other agricultural-related technology innovation,such as new soil remediation technology,seed cultivation technology,crop resistance technology,high-value agricultural technology and agricultural waste utilization technology should be vigorously promoted. The transformation of agricultural organization form and upgrade of agrochemical service are also indispensable. In the development of "Sixth Industry",agrochemical industry will usher in new development opportunities. With the application of new chemical products and advanced technology,the resulting social and economic benefits will be very considerable.
    Current status and evaluation of hydrogen pinch technology
    SUN Xiaoyan, SONG Hongyang, LIU Boqian, XIANG Shuguang
    2017, 36(04):  1165-1172.  doi:10.16085/j.issn.1000-6613.2017.04.002
    Abstract ( 417 )   PDF (618KB) ( 509 )  
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    Hydrogen pinch technology is an important method of hydrogen network optimization with the advantage of simple,intuitive,efficient and easy to understand. It already has mature and stable development in resolving the hydrogen network bottlenecks since the late 1990s. This paper recommended the basic principle of the hydrogen pinch. Hydrogen pinch technology method includes hydrogen surplus graphical method,rigorous graphical targeting, pure hydrogen load versus flow rate diagram graphical method,source composite curve graphical method,deficit diagram of multiple impurities,and so on. The paper summarized the current status and research progress of these methods. Then, various methods to obtain the advantages and disadvantages were compared and evaluated. Finally, the paper discussed the future study of hydrogen pinch technology, which are multiple constraints,dynamics modeling and optimization of flexible design.
    Optimization of water-using network in batch processes involving regeneration operation
    CHEN Yanling, LIU Linlin, HE Zhancong, DENG Chao, DU Jian
    2017, 36(04):  1173-1179.  doi:10.16085/j.issn.1000-6613.2017.04.003
    Abstract ( 299 )   PDF (605KB) ( 341 )  
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    Currently,the problem of water scarcity and water pollution is increasingly severe. It is an effective way of fresh water conservation and environmental protection by reusing regenerated wastewater. In order to achieve reasonable utilization of process sources with different qualities for maximum reuse of water in batch processes,a superstructure of water-using network was proposed involving source-sink,source-intermediate storage tank-sink,source-continuous regeneration system-sink and source-wastewater disposal system. The mathematical formulation is based on a continuous time representation. With multi-objective optimization design method,design problems for minimizing the freshwater consumption,the regeneration rate of the regeneration unit and the number of intermediate storage tanks can be achieved in turn. Finally,an applicable network configuration with the minimum amount of freshwater consumption and wastewater discharge was obtained. Additionally,in consideration of the actual production process of multiple batch cycles,this paper focused on the design,analysis and optimization problem of water-using network from start-up to the steady state. A case study was solved to demonstrate the effectiveness of the proposed approach.
    Heat exchange network synthesis and optimization for batch process considering scheduling
    DENG Chao, LIU Linlin, LIANG Xinyuan, CHEN Yanling, DU Jian
    2017, 36(04):  1180-1186.  doi:10.16085/j.issn.1000-6613.2017.04.004
    Abstract ( 282 )   PDF (1100KB) ( 296 )  
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    Heat exchange network(HEN) synthesis is an important part of chemical process system engineering. Time,equipment and scheduling should be considered regarding to the design of the HEN for batch process,which brings complexity to the design of batch process. This paper focused on direct heat integration for multi-stage batch process considering scheduling. By using overlapping and non-overlapping operation and adjusting the limited cycle time,the opportunity of direct heat exchange was increased and the equipment idle time was reduced. Thus,three different production plans were obtained. Then for each production plan,an initial HEN was synthesized using heuristic method. Based on this method,HEN structure evolution was conducted by using the proposed progressive evolution rules and the trade-off between utility cost and equipment cost. After that,the number of heat exchangers and the branch streams was decreased. HEN with minimum total annual cost and less heat exchangers was gotten. The comparison between the three plans shows the scheduling effect on the HEN synthesis. Finally,an example was used to show the application and effectiveness of the proposed method.
    Estimation models and mathematical analysis of particle transportation in a rotary dryer
    LI Miaoling, ZHAO Hongxia, YAO Yongyu
    2017, 36(04):  1187-1191.  doi:10.16085/j.issn.1000-6613.2017.04.005
    Abstract ( 310 )   PDF (582KB) ( 603 )  
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    At present,the research method of material movement in the cylinder of a rotary dryer is mainly to set up the held and thrown material models of a lifting plate and the residence time model of materials in the cylinder body. But the most formulas depend too much on the empirical constants,and the physical meaning is not clear. Based on the thrown movement law of materials,the space model of the particle transportation in a rotary dryer is established. First,the motion rule was studied for the solids in the flight rotary dryer. The paths of fall of the particles in the drum were drawn by Matlab drawing toolbox and showed on the three-dimensional image. Then,the analytic mathematical models of the motion were proposed for the space particle. The equations of residence times were deduced. The proposed estimation models were determined by considering the air drag on the solids in the drum,as well as the inclined angle,the rotation speed and the filling rate of a drum. The calculation formula of residence times was with a clear and definite physical meaning. The residence time calculated by using the proposed equation was compared to the average experimental values from the engineering example and the results obtained by calculations using equations proposed in the literature. The equation proposed for predicting residence time generated accurate estimations.
    Research on orifices diameter of calandria liquid distributor used in offshore deacidification tower with different spray densities
    TANG Jianfeng, CUI Jian, XIU Yunfei, YANG Wengang, JIN Xinming, ZHANG Weiming
    2017, 36(04):  1192-1201.  doi:10.16085/j.issn.1000-6613.2017.04.006
    Abstract ( 308 )   PDF (1509KB) ( 493 )  
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    In recent years,floating liquefied natural gas(FLNG) has become a new field that attracts increasing attention. Study on structure design of liquid distributor which is one of the most important tower internals under the condition of sloshing is little. A calandria liquid distributor with diameter of 1.2 meters with 52 orifices was studied in this paper by utilizing experimental device consisting of a shaking platform and a water circulation system. Hydraulic experiments were carried out under the condition of static situation,roll 5 degrees and pitch 5 degrees. By changing the liquid distributor's spray density,the distribution performance's changes of the liquid distributor and its branch pipes with different orifice diameters in sloshing condition were analyzed. Combining with reasonable range of outlet velocity and outlet flow ununiformity's increasing degree that compared with static situation,optimal outlet diameter design with various spray densities under sloshing condition within 5 degrees was determined. Results showed that calandria liquid distributor with small-size orifices is influenced less by sloshing condition,but its outlet velocity is big;under the sloshing condition within 5 degrees,the orifice diameter is designed to 4mm,6mm and 8mm when the spray density is about 4.4m3/(m2·h),8.8m3/(m2·h) and 13.2m3/(m2·h),which can not only ensure that the outlet velocity is reasonable,but also can keep the good uniform performance of calandria liquid distributor.
    Effect of operation parameters on removal efficiency of fine particles in a water-sparged aerocyclone
    CHENG Zhiliang, QUAN Xuejun, LI Shuo, LI Ruiheng, XU Fei
    2017, 36(04):  1202-1208.  doi:10.16085/j.issn.1000-6613.2017.04.007
    Abstract ( 262 )   PDF (737KB) ( 450 )  
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    With the rapid development of industry in China,mass of fine particulate matter is emitted to the air,which is a big threat to the environment and public health. In order to overcome the shortage of low efficiency of traditional wet dust collection devices,a new device of water-sparged aerocyclone(WSA) was used for removal of model PM2.5 sample of talcum powder with average particle size of 1.56 μm. The effects of operation parameters of initial concentration of dust,liquid jet velocity,gas inlet velocity on the total removal efficiency(η) of dust were investigated. Besides, experimental data was then summarized and analyzed to obtain the relationship between operating parameters and the removal efficiency. Results showed that the highest removal efficiency of fine particulate matter with 74.15% of the PM2.5 was over 93%. When the WSA was used to treat the dusty gas,it is particularly effective to the particulate matter whose diameter is bigger than 1.8 μm,the removal efficiency can even reach to 100%. The removal efficiency increased with the increase of initial concentration of dust,liquid jet velocity and gas inlet velocity,which follows the formula of η=133.61×Reg0.026×Rel0.027×(cs/ρs)0.065. The formula was proved to be useful in forecasting the removal performance of dust of the WSA. This investigation could develop a new process in removing industrial fine particulate matter.
    Recovery of ionic liquid from aqueous solution by ion-exchange resin
    SUI Hong, NIU Yaqi, LI Xingang, HE Lin
    2017, 36(04):  1209-1216.  doi:10.16085/j.issn.1000-6613.2017.04.008
    Abstract ( 358 )   PDF (710KB) ( 358 )  
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    The ionic liquid enhanced bitumen recovery from oil sands has been considered a promising process for the unconventional oil production. However,the recovery of ionic liquid from the residual solids is a challenge due to the high energy consumption if the direct distillation is applied. A new technology was proposed to pretreat the ionic liquids solution with ion-exchange resins (AMBERJET 1200Na). The concentrated ionic liquid was further separated by distillation. The optimal operational conditions were obtained by adjusting parameters of adsorption and desorption. The mechanism of the adsorption process was also analyzed. To confirm the above results,the real ionic liquids solution obtained from the water washing was applied as sample which was processed under the above optimal conditions. The results showed that the efficiencies of adsorption,desorption and recovery were over 97%,93% and 91%,respectively when 5g resin dosage was used to treat the ionic liquid solution (10g/L) at 293K for the adsorption and 333K for desorption. Finally,it was found that this process could save energy by 45% compared with the direct distillation under laboratory conditions.
    Mixing performance in a miniature conical twin screw extruder with batch filling
    CHEN Shichang, ZHANG Xianming, XU Junjie, CHEN Wenxing, FENG Lianfang
    2017, 36(04):  1217-1223.  doi:10.16085/j.issn.1000-6613.2017.04.009
    Abstract ( 328 )   PDF (715KB) ( 479 )  
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    The circulatory mixing in a miniature conical twin screw extruder(MCTSE) under the condition of batch filling was evaluated numerically using finite element modeling. The simulation was implemented with mesh superposition technique to generate velocity profiles and particle trajectories for the extrusion process of polymer melt. Based on the statistical analysis of tracking particles,the dispersive mixing was evaluated using shear stress and mixing index,and the distributive mixing was assessed using the length of stretch and the scale of separation. The mixing performance in different screw pitch and rotating speed were also examined. The results showed that the mixing of MCTSE was dependent on stretching flow cooperation with shear flow. Both the dispersive mixing and distributive mixing were improved by either increasing the rotating speed of screw or decreasing the screw pitch,yet an opposite tendency was displaying for the mixing efficiency. The preference was given to the proper process rather than the screw structure of MCTSE on the basis of the composite analysis of different mixing parameters.
    Analysis of biomass gasification in bubbling fluidized bed with a revised bubble-based energy minimization multiscale drag model
    CHEN Juhui, YIN Weijie, WANG Shuai, YU Guangbin, HU Ting, LIN Feng
    2017, 36(04):  1224-1230.  doi:10.16085/j.issn.1000-6613.2017.04.010
    Abstract ( 299 )   PDF (1525KB) ( 322 )  
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    Based on the framework of two-fluid model,a revised bubble-based energy minimization multiscale(EMMS) drag model was proposed. Incorporating chemical kinetics method,the biomass gasification model was presented for simulating the biomass gasification process in the bubbling fluidized. The simulations with Bubble-based EMMS drag model that accounted for the effect of bubble in mesoscale which enhances the heterogeneous reaction between gas phase and solid phase were in good agreement with the experimental data. The simulation results provided the distributions of particles concentration,velocity vector,molar fractions of gas phase,and mass fractions of carbon and ash. The effect of equivalence ratio on biomass gasification process in the bubbling fluidized bed was analyzed. In general,the gas products tend to decrease with the increase of equivalence ration. Analysis found that the production of H2 and CH4 has strong correlation with the equivalence ratio with goodness of fit(adj. R2) above 0.99. As for CO and CO2,their correlations with the equivalence ratio can be better predicted by cubic polynomials. And,CO first decreases significantly as equivalence ratio increases,then becomes flat and finally decreases afterwards. CO2,however,follows the opposite trend.
    Optimization and reformation of heat exchanger network for wax oil hydrocracking unit by pinch technology and exergy analysis
    LI Zhonghua, XIAO Wu, HE Gaohong, DU Yanze, FANG Xiangchen, LUO Li
    2017, 36(04):  1231-1239.  doi:10.16085/j.issn.1000-6613.2017.04.011
    Abstract ( 337 )   PDF (1104KB) ( 493 )  
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    A wax oil hydrocracking process unit with annual capacity of 1.5 million tons in a refinery was simulated using Aspen Plus. The unit included single segment series,cold high pressure column,and light hydrocarbon absorber vacuum tower. Based on the basic production data of wax oil hydrocracking units,Aspen Plus software was used to establish a strict mathematical model for each module in the process. By adjusting the model parameters,the simulation results and calibration data were in a good agreement. Then thermodynamic parameters of different streams were obtained from the simulation. Based on the simulation,the "bottleneck" of the heat exchanger network for the process was identified using pinch analysis.,With the premise of not changing the main equipment of the system,the tuning and simulation of the existing heat exchanger network were achieved for the energy-saving program. The effective energy analysis method was also used to evaluate the heat exchange network before and after the reformation. After the tuning,the amount of hot utility was the 25709kW that is 42.2% less than original process;the amount of cold utility was 29863kW that was 38.5% less than the original process. Overall,the transformation program would save energy 17.19kgEO/t total exergy loss of the heat exchanger network would be reduced to 8477kW from 13530kW with the total exergy loss decreased by 37.35%.
    Deep removal of impurities from phosphogypsum
    ZHAO Hongtao, BAO Weijun, SUN Zhenhua, LI Songgeng, LI Huiquan, LIN Weigang
    2017, 36(04):  1240-1246.  doi:10.16085/j.issn.1000-6613.2017.04.012
    Abstract ( 473 )   PDF (2252KB) ( 924 )  
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    To deeply remove the impurities and improve the quality of phosphogypsum(PG),three PG purification methods,including water washing,acid pickling,and acid pickling coupling solvent extraction,were comparatively analyzed according to the results of characterization by XRF,XRD,SEM and whiteness. Results showed that a small amount of soluble phosphorus,magnesium compounds and part of soluble silicon,fluorine compounds on the surface of PG could be removed by water washing,while almost all of the acid soluble compounds containing Si,Al,Fe,F and K impurity elements in PG could be removed by acid pickling. It was found that the main mineral phase of CaSO4·2H2O in PG underwent the dissolution and recrystallization to form CaSO4both in water washing and acid pickling process,while the transformation speed was much faster in the latter. Moreover,when the organic solvent tributyl phosphate(TBP) was added to the acid pickling process,all of the impurities in PG involving the acid insoluble impurities,such as quartz,iron sulfide,inorganic carbon black,and the barely soluble impurities,such as K2SiF6 and aluminum fluoride with crystal water,can be effectively removed. The clubbed CaSO4 with the purity and whiteness of more than 99% and 92%,respectively,could be obtained by this acid pickling coupling with solvent extraction technique,which would provide a new way for the comprehensive utilization of PG.
    Recent progress in research and application of DBBF additive in preparation and combustion process
    CUI Xuyang, YANG Junhong, LEI Wanning, HUANG Tao, WANG Pufang, JIA Chen
    2017, 36(04):  1247-1257.  doi:10.16085/j.issn.1000-6613.2017.04.013
    Abstract ( 435 )   PDF (1451KB) ( 817 )  
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    The screening and application of densified biomass briquetting fuel(DBBF) additive is of great importance for the large-scale preparation and efficient combustion of DBBF. At present,the relevant literature reviews are more concentrated on the DBBF,its preparation,and combustion equipment. Based on emissions management and efficient combustion,DBBF modification,fuel additives preparation,and functional classification and mechanism,this paper summarized the research progress of DBBF additives for adhesives,anti-corrosion additives,and accelerant. DBBF binders have high selectivity and low price,but the mechanical strength of the fuel needs to be improved. DBBF additives for anti-corrosion and anti-settling are abundant,but their work efficiencies are low. There were few DBBF accelerants.Their combustion mechanism is not clear. And there is no unified standards for research and development. The accelerantadditive can effectively improve the combustion performance of DBBF. Finally,the principles of selecting DBBF common additives and the future research directions in the development of new DBBF additives are clearly presented.
    Simulation and analysis of modified comprehensive utilization system of Hua-dian oil shale using gaseous heat carrier
    BAI Jingru, WANG Lintao, ZHANG Qingyan, BAI Zhang, WANG Qing
    2017, 36(04):  1258-1264.  doi:10.16085/j.issn.1000-6613.2017.04.014
    Abstract ( 272 )   PDF (555KB) ( 290 )  
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    The comprehensive utilization system of Hua-dian oil shale,which uses gaseous heat carrier technology,is an important utilization method of oil shale. Some parts of the system are modified in this paper,and the retorting gas and the syngas produced by the gasifier are fed into the gas-steam combined cycle power generation system. Meanwhile,the fuel gas from the gas turbine is used to heat the gaseous heat carrier. The system is simulated with Aspen Plus,and the balance of energy and exergy is analyzed with the simulated data. The results show that the total energy efficiency and exergy efficiency of the system reach 58.23% and 60.18% respectively,which is much higher than the original system. Furthermore,the energy efficiency and exergy efficiency of the main units in the modified system are both higher than 60%. Further analysis suggests that the increase in mass fraction of the oil shale for retorting can improve the yield of liquid fuel of the system effectively. Besides,although the electricity output of the system is reduced,the total exergy efficiency will increase obviously.
    Experimental study on promoting HCFC-141b hydrate formation with organic phase change material
    ZHU Minggui, SUN Zhigao, YANG Mingming, LIU Minrui, LI Juan, LI Cuimin, HUANG Haifeng
    2017, 36(04):  1265-1269.  doi:10.16085/j.issn.1000-6613.2017.04.015
    Abstract ( 275 )   PDF (504KB) ( 598 )  
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    In order to solve the problem of long induction time and low growth rate for hydrate formation in quiescent systems,capric acid(CA)and lauryl alcohol(DE) composite phase change material is used as promoter for HCFC-141b hydrate formation. The effect of composite phase change material on the HCFC-141b hydrate formation is investigated experimentally. Emulsion of HCFC-141b is prepared using high-speed stirring. Emulsion increases the contact area between HCFC-141b molecules and water molecules and promotes hydrate formation. The promoting effect is the best with the shortest induction time,the largest temperature rise and the fastest growth of hydrate formation by adding 1% CA-DE phase material under experimental conditions. The experimental results show that the induction time of hydrate formation has a certain randomness. HCFC-141b hydrate could form within 1h under 0.2℃ and 1℃. The induction time of hydrate formation decreases,the rate of hydrate growth increases and the randomness of hydrate formation decreases with the reduction of the temperature.
    Research progress in the removal of cooking oil fumes by catalytic combustion
    HUANG Yonghai, YI Honghong, TANG Xiaolong, ZHAO Shunzheng, FENG Tiecheng
    2017, 36(04):  1270-1277.  doi:10.16085/j.issn.1000-6613.2017.04.016
    Abstract ( 304 )   PDF (449KB) ( 591 )  
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    The pollution by cooking oil fumes is harmful to both environment and human body. This paper reviewed and summarized the main purification methods of cooking oil fumes in China in recent years as well as their individual features. Compared with other treatment technologies,catalytic combustion is green and of high efficiency which can purify a variety of organic waste gases. So,it has become an important research direction of cooking oil fumes treatment technology. In this paper,the recent research progress in cooking oil fumes purification by catalytic combustion technology was summarized. The recent progress of noble metal and metal oxides catalysts used in catalytic combustion technology were also reviewed. In addition,this paper expounded the deactivation and regeneration of the catalysts. Finally,regarding the existing problems,we put forward the prospect of the catalytic combustion technology and pointed out that the development of new catalyst is the key to this technology.
    Advance in BTX production increase technology from C9+ heavy aromatics
    ZANG Jiazhong, GUO Chunlei, FAN Jingxin, WANG Yinbin, YU Haibin
    2017, 36(04):  1278-1287.  doi:10.16085/j.issn.1000-6613.2017.04.017
    Abstract ( 386 )   PDF (776KB) ( 730 )  
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    With the newly built aromatic combining plant and large-scale ethylene plants and those with capacity expansion revamping,the C9+ heavy aromatic byproducts yield will greatly increase in the future. The conversion of C9+ heavy aromatics to BTX by aromatics increase technology is of great significance for the enterprises to tap potentials and expand aromatic raw materials. The technologies of increasing BTX from reforming C9+ and pyrolysis C9+ heavy aromatics are reviewed,including reaction principles,processes,catalysts,advantages and disadvantages for themo-hydrodealkylation, hydrodealkylation, non-hydrodealkylation and two-stage hydrocracking technologies. Meanwhile,the prospects and future development of each technology are also presented. The article points out that both the increasing aromatic technology from reforming C9+ and pyrolysis C9+ heavy aromatics still have a lot of problems,and innovation of process and catalyst are needed to improve the technology. Catalytic material is the key of the technology innovation and development,and in the future the reaction mechanism,catalyst deactivation mechanism and process engineering issues should be integrated to develop new efficient catalytic materials,which can promote the innovational development of BTX increase technology from C9+ heavy aromatics.
    Effect of preparation method of ZrO2 support on catalytic performance of MoO3/ZrO2 for sulfur-resistant methanation
    YANG Xia, QIN Shaodong, LI Jiabo, SUN Shouli
    2017, 36(04):  1288-1293.  doi:10.16085/j.issn.1000-6613.2017.04.018
    Abstract ( 284 )   PDF (3425KB) ( 300 )  
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    ZrO2 was prepared via precipitation method and then used as the support of Mo catalysts for CO methanation in the presence of H2S. The impact of post precipitation procedures of ethanol-washing and digestion(aging in hot ethanol) on the evolution of textural,structural and morphological properties of zirconia was investigated. The physicochemical properties of ZrO2 supports and MoO3/ZrO2 catalysts were characterized by nitrogen adsorption-desorption,XRD,TEM and XPS. The results indicated that the post precipitation treatment was an effective means to achieve zirconia support with large specific surface area,and uniform and small particle size. The catalytic performance of the MoO3/ZrO2 catalysts was improved with ZrO2 prepared by digesting at high temperature,which could be related to the degree of sulfidation of Mo species and the enhancement of dispersed MoS2 active sites.
    Study on catalyst for continuous catalytic amination of TMEDA
    WU Jun, QIAN Junfeng, SUN Fu'an, WU Zhong, CUI Aijun, HE Mingyang, CHEN Qun
    2017, 36(04):  1294-1300.  doi:10.16085/j.issn.1000-6613.2017.04.019
    Abstract ( 354 )   PDF (539KB) ( 359 )  
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    A compound catalyst with Cu/Ni as the main activate component is applied for continuous catalytic amination DMEA to TMEDA. The influences of catalyst carrier type,Cu/Ni molar ratio,loading amount,additives,roasting time and temperature on the performance of the catalyst were investigated. The best preparation conditions of the catalyst were as follows:with the γ-Al2O3 ball as the carrier,Cu:Ni:Mn=4:1:0.2(mole ratio),the load amount 20%,and roasting 6h at 500℃. Under the conditions of the reaction temperature of 240℃,atmospheric pressure,amine alcohol molar ratio 1:1,space velocity of 0.12h-1,hydrogen speed of 30 mL/min,the conversion rate of DMEA and the selectivity of TMEDA could achieve 92.8% and 82.9%,respectively. Through 500h life test,the conversion rate and selectivity were stable and maintained at above 90% and 80%,respectively. The experimental results showed that the catalyst had excellent catalytic activity and stability.
    Preparation of nano spinel CuFexCo2-xO4and its application in nitrophenol catalytic reduction
    ZHAO Shiduo, REN Shucheng, LI Qiming, LI Fang, LIANG Zhihua
    2017, 36(04):  1301-1305.  doi:10.16085/j.issn.1000-6613.2017.04.020
    Abstract ( 271 )   PDF (1967KB) ( 432 )  
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    Water pollution,especially caused by p-nitrophenol,has drawn more and more attention in recent years. To solve the problem,catalytic reduction of p-nitrophenol into p-aminophenol is proposed,however,it requires catalyst of high activity and easy to recovery. Nano spinel CuFexCo2-xO4 recyclable catalysts(CuFe2O4、CuFeCoO4、CuCo2O4) are prepared via a gel-burning method,and their catalytic activities are investigated in the catalytic nitrophenol reduction.XRD characterization indicates that CuFe2O4,CuFeCoO4 and CuCo2O4 catalysts all have excellent spinel phase structure. Micro-morphologies of nano spinel CuFe2O4,CuFeCoO4 and CuCo2O4 catalysts are checked using SEM. SEM images showed that nano spinel CuCo2O4 catalyst has smaller particle size and higher dispersions than those of CuFe2O4 and CuFeCoO4 catalysts. In the catalytic nitrophenol reduction,nano spinel CuCo2O4 catalyst exhibits much higher catalytic activity than CuFe2O4 and CuFeCoO4 catalysts.
    Surface modifications for preparation of MOF thin films
    QIN Xi, SUN Yuxiu, WANG Naixin, XIE Yabo, LI Jianrong
    2017, 36(04):  1306-1315.  doi:10.16085/j.issn.1000-6613.2017.04.021
    Abstract ( 478 )   PDF (4172KB) ( 1479 )  
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    This review summarizes the recent research progress of surface modification methods for the preparation of metal-organic framework(MOF) thin films. MOF,featured by designable structures,tunable pore sizes and functions and so on,is considered as attractive membrane material for gas separation. Forming interfacial interaction between the MOF crystals and substrates is the key to fabricate a continuous and compact MOF film. Surface modifications can improve the physical/chemical properties of the substrates and enhance the interaction force between MOF crystals and substrates. In this review,three main surface modification methods for the preparation of MOF thin films are highlighted,including organic molecular modification,inorganic compound modification,and MOF seed modification. Particularly,the modification mechanisms of different modification methods are emphasized,and the influences of the modification methods on the preparation and gas separation performance of MOF thin films are analyzed. Due to the diversity of MOF and complexity of the film formation,single modification can't always produce dense and uniform MOF membrane. Therefore,we propose that it will be an important development direction for the preparation of MOF films to combine different modification methods according to the properties of the MOF and the substrate.
    Progress of chemical sensors based on metal-organic frameworks (MOFs)
    LI Ying, ZHANG Hongxing, YAN Kele, HU Xuyao, JIA Runzhong, ZOU Bing, XIAO Anshan
    2017, 36(04):  1316-1323.  doi:10.16085/j.issn.1000-6613.2017.04.022
    Abstract ( 375 )   PDF (2267KB) ( 1111 )  
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    Recently,chemical sensors based on MOFs have aroused a great deal of attention. The features of MOFs materials such as tunable pore size and huge specific surface area can improve the detection selectivity and sensitivity of chemical sensors. Signal transduction is one of major challenges which largely limits the implementation of chemical sensors based on MOFs. Signal transduction methods are summarized in this review,including optical sensors(interferometry,localized surface plasmon resonancem,colloidal crystals,solvatochromism,luminescence-based sensing),impedance spectroscopy,electromechanical sensors(surface acoustic wave sensors,quartz crystal microbalance and microcantilevers). Finally,application prospect of chemical sensors based on MOFs is proposed,and a promising concept for improving sensitive and selective detection is to synthesize more conductive MOFs materials and couple MOFs with vibrational spectroscopy or other analytical techniques that can provide a molecular fingerprint.
    Synthesis of functionalized polyhedral oligomeric silsesquioxane and its application in silicone
    WANG Feng, MU Qiuhong, PENG Dan, ZHANG Fangzhi, LI Jinhui, ZHAO Ning, YU Yitao, LI Bing
    2017, 36(04):  1324-1332.  doi:10.16085/j.issn.1000-6613.2017.04.023
    Abstract ( 375 )   PDF (782KB) ( 693 )  
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    Polyhedral oligomeric silsesquioxane(POSS) is a kind of nanoscale compound with cage-like organic-inorganic hybrid structure,with many unique physical and chemical properties. Functionalized POSS javascript:void(0);can be used in the synthesis and modification of silicone materials to improve their physical and chemical properties,and broaden their applications. In this paper,the synthesis methods of POSS were reviewed,with the emphasis on the functionalized POSS,including octaphenyl-POSS,octavinyl-POSS,octahydro-POSS,epoxy-POSS,amino-POSS,isocyanate-POSS and mono-functionalized POSS. In addition,the application progress of functionalized POSS in silicone was summarized from aspects of both physical and chemical modification. POSS has shown great potential in the field of polymer modification,and the application trend of functionalized POSS in silicone materials was also prospected. In the future,with the appearance of new POSS compounds,the application of functionalized POSS in silicone materials would achieve greater progress.
    Advances in hollow MOFs
    ZHANG Chunhua, CHEN Rizhi, XING Weihong
    2017, 36(04):  1333-1341.  doi:10.16085/j.issn.1000-6613.2017.04.024
    Abstract ( 447 )   PDF (5042KB) ( 995 )  
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    H_MOFs have attracted considerable interest and found potential applications in many fields due to their special properties such as high surface area,low density and hollow structure,and the related reseach has been an important direction of MOFs materials. This article mainly featured recent research progress towards various preparation methods of H_MOFs,with the focus on the hard-template routes including polystyrene and Cu2O,the soft-template routes including emulsion-based interfacial synthesis and gas-liquid interfacial,and the template-free routes including Ostwald Ripening and Kirkendall effect were analyzed in detail. And the advantages and disadvantages of these methods,were discussed respectively. Applications of H_MOFs in gas adsorption and separation,catalysis,and potential applications of H_MOFs in biomedical,magnetic separation and environment protection were also discussed. The preparation of novel and highly stable H_MOFs materials with versatile morphology and good crystallinity,the precise control of shell thickness and the development of preparation methods of H_MOFs were proposed as the main future research and development directions of H_MOFs.
    Progresses in exploration and application of porous liquid materials
    LI Yanlin, DUAN Zunbin, HUO Tian, ZHU Lijun, XIANG Yuzhi, XIA Daohong
    2017, 36(04):  1342-1350.  doi:10.16085/j.issn.1000-6613.2017.04.025
    Abstract ( 472 )   PDF (1847KB) ( 635 )  
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    Porous liquid materials refer to a certain type of liquids with internal unit molecular possessing stable,permanent,shape fixed cage cavities,which overcome the storage and application limitations of porous solid materials. In this paper,the background of porous liquid materials was firstly reviewed,and the development of the materials was presented. Then,according to different structure features,the porous liquid materials were classified into two categories,and theirs preparation methods were given in detail. Moreover,the applications of porous liquid materials include gas adsorption and separation as well as host-guest chemistry. At last,the future development of them was prospected. Porous liquid materials are expected to be used in areas of catalysis,photoelectric material,petrochemical industry,and biology. The synthesis and application of porous liquid materials will become a research focus.
    DNA-base regulation of Pt nanocrystals: morphology and catalytic activity for hydrogenation
    SUN Xiaoqing, LI Guozhu, LI Xiaodi, WANG Li, ZHANG Xiangwen
    2017, 36(04):  1351-1357.  doi:10.16085/j.issn.1000-6613.2017.04.026
    Abstract ( 236 )   PDF (5828KB) ( 571 )  
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    Pt nanocrystals(NCs) have been used as the catalyst for many hydrogenation reactions due to their good catalytic performance. Their catalytic activity and selectivity are strongly dependent on their nanostructure(morphology and size). According to Gibbs-Wulff theory,the morphology and size of NCs can be effectively controlled by certain capping agent. In this paper,various biomolecules,including DNA basic groups (adenine,guanine,thymine,cytosine) and corresponding nucleosides,have been employed as capping agent to control the size and shape of Pt NCs. NaBH4 has been used to reduce platinum precursor(H2PtCl6) to prepare Pt NCs in water solution. The reduction of p-nitrophenol(p-NIP) by H2 was employed as model reaction to evaluate the catalytic performance of as-prepared Pt NCs. Experimental results show that capping agent of biological molecules has a significant effect on the regulation of Pt NCs. Pt NCs with multiple morphologies and sizes have been successfully prepared. Simultaneously,the as-prepared Pt NCs showed precisely controllable activity for the hydrogenation of p-NIP. The TOFave of the Pt NCs regulated by guanosine,adenine,thymine are twice as much as that of the catalyst without any capping agent. Among all the catalysts,the adenine capped one showed the highest catalytic activity.
    Grey correlation analysis of influencing factors of polyethylene thermo-oxidation aging based on AHP-DEA
    DAI Jun, YAN Hua, WANG Xuemei, GUO Junjun, HU Zhide, YANG Jianjian
    2017, 36(04):  1358-1365.  doi:10.16085/j.issn.1000-6613.2017.04.027
    Abstract ( 305 )   PDF (497KB) ( 282 )  
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    In this work,eight representative types of polyethylene(PE) samples were selected and exposed in accelerated thermo-oxidation environment for up to 64 days. Taking analytic hierarchy procedure(AHP) based grey relational analysis method as the central model and data envelopment analysis(DEA) as the auxiliary model,we quantitatively studied the influence of different factors on PE thermo-oxidation properties by calculating the correlation coefficient between different factors(thermo-oxidation aging time,temperature,density,crystallinity,molecular weight) and PE bending strength. The results showed that lower of density,higher degree of crystallinity and wider molecular weight distribution of PE results in faster decrease of the bending strength which was mainly concentrated in the early and latter part of aging. The order of relational degree between different factors and PE bending strength was crystallinity,molecular weight distribution(MWD),density,aging temperature and aging time. In the internal factors,crystallinity had the greatest influence on PE thermo-oxidation aging property,with a correlation degree of 2.857. The higher the crystallinity,the more the flaw in PE,which facilitates the oxidation under thermo-oxidation environment and the aging phenomenon gets more severe.
    Methyl methacrylate polymerization in the channels of modified halloysite nanotubes by ARGET ATRP
    CHEN Mingsen, ZHOU Hongwang, WANG Luhai, ZHANG Faai
    2017, 36(04):  1366-1373.  doi:10.16085/j.issn.1000-6613.2017.04.028
    Abstract ( 242 )   PDF (2979KB) ( 319 )  
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    Free radical polymerization within confined space is expected to obtain products with special properties or new materials. Halloysite nanotubes(HNTs) were modified by vinyl triethoxylsilane(KH151),3-aminopropyltriethoxysilane (KH550),3-glycidoxypropyl-trimethoxysilane(KH560),and 3-methacryloxypropyltrimethoxysilane(KH570),respectively,and used as "confined space" to polymerize methyl methacrylate by activators regenerated by electron transfer for atom transfer radical polymerization(ARGET ATRP). The modified HNTs(HNTs-M),HNTs-M/PMMA composites and PMMA obtained from the channels of HNTs-M were characterized by X-ray powder diffraction(XRD),transmission electron microscope(TEM),scanning electron microscopy(SEM),nitrogen adsorption measurements,gel permeation chromatography(GPC),fourier transform infrared spectroscopy(FTIR),thermogravimetry analysis(TGA),and hydrogen nuclear magnetic resonance (1H NMR),respectively. The results showed that the specific surface area,pore volume and pore size of HNTs,HNTs-M and HNTs-M/PMMA composites were decreased in turn,but there was no change in crystal structure,indicating that the PMMA in the channels was of amorphous morphology. Compared with conventional polymerization of MMA,the PMMA in channels possessed higher molecular weight,thermostability,and isotactic structure content and narrow molecular weight distribution,but decreased syndiotactic structure content.
    Preparation,characterization of HTMAC/KH550/bentonite adsorbent and its adsorption behavior on methyl orange wastewater
    YAO Pei, LI Shubai, LIU Yuan, ZHANG Qimeng, JI Conglan, NIE Huali
    2017, 36(04):  1374-1380.  doi:10.16085/j.issn.1000-6613.2017.04.029
    Abstract ( 295 )   PDF (1308KB) ( 557 )  
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    Organobentonites were prepared by modifying calcium bentonite using hexadecyltrimethyl-ammonium chloride(HTMAC) and silane coupling agent(KH550) as intercalation agents. The characteristics of swelling volume,colloid valence,and ethylene blue adsorbed were measured. Organobentonites were characterized with fourier transform infrared(FTIR),X-ray powder diffraction(XRD),scanning electron microscope(SEM) and brunauer-emmett-teller(BET). Results showed that the ability of dispersion and adsorption of organics increase with the increase of colloid valence and ethylene blue adsorbed. Under the co-modification of HTMAC and KH550,the modified reagents has been intercalated to the layer of bentonite,and the d001 values increase from 1.53nm to 2.89nm. The N2 adsorption-desorption isotherm exhibited that organobentonite has type Ⅳ isotherm with a clear H3 hysteresis loop,which indicated that HTMAC/KH550/bentonite was a mixed microporous/mesoporous

     

    material. Organobentonites were used to treat methyl orange wastewater. The effects of dosage,flocculation time,adsorption temperature and pH were investigated. Result showed that the highest removal rate of methyl orange wastewater was 89.8%. The optimum operationcondition were dosage of organobentonite 2g/L,flocculation time 30min,pH7-8 and adsorption temperature 20℃. Adsorption equilibrium studies showed that methyl orange adsorption follows the Langmuir model. In addition,the maximum adsorption capacity of the organobentonite was determined to be 71.53mg/g. HTMAC/KH550/bentonite is a kind of high adsorption capability adsorbent. It can provide a new method for dye removal.

    Esterified cellulose nanocrystals/poly(urea-urethane) self-healing materials based on aromatic disulfide bonds
    TANG Lirong, WANG Weibin, WANG Qinghua, ZHUANG Senyang, CHENG Cuixia, HUANG Biao
    2017, 36(04):  1381-1387.  doi:10.16085/j.issn.1000-6613.2017.04.030
    Abstract ( 316 )   PDF (4424KB) ( 490 )  
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    In this study,the esterified cellulose nanocrystals/poly(urea-urethane)(E-CNCs/PUs) self-healing materials were prepared using polypropylene glycol 4000(PPG-4000) and isophorone diisocyanate(IPDI) as raw material,bis (4-aminophenyl) sulfide as crosslinking agent,and esterified cellulose nanocrystals as reinforcement. The mechanical properties,thermal properties,surface chemical structures,and self-healing properties were investigated. The results show that E-CNCs/PUs were self-healing effectively at room temperature without any external interventions,which confirms that bis(4-aminophenyl) disulfide can be effectively used as a dynamic cross-linker for the design of self-healing poly(urea-urethane) material. The maximum tensile strength of E-CNCs/PUs could reach 5.71MPa when the additive amount of E-CNCs was 0.1%,which was increased by 43.11% compared with pure poly(urea-urethane). E-CNCs/PUs composite materials present high tensile strength,elasticity,and malleability. The additive of E-CNCs just has a small influence on the thermal properties of E-CNCs/PUs self-healing materials.
    Effects of additive PEG on the properties of CPVC/PVB blended membranes
    LIU Qianwen, ZHANG Xiaojuan, GU Qianqian, WANG Jun
    2017, 36(04):  1388-1394.  doi:10.16085/j.issn.1000-6613.2017.04.031
    Abstract ( 330 )   PDF (3352KB) ( 395 )  
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    Effect of additive PEG molecular weights on the microstructures and properties of CPVC/PVB blended membranes was discussed in this paper. It was found that the finger-like macrovoids structure in the microstructures of CPVC/PVB blended membranes cross section was replaced by porosity microstructure when the molecular weight was less than 6000. The finger-like macrovoids structure reappeared when the molecular weight was up to 6000 and the cross section microstructure was close to that of CPVC/PVB blended membranes which were free of additive. The microstructure of membrane surface was porosity structure when the molecular weight was 400 and 600, respectively. With the increase of molecular weight, the microstructure of membrane surface tended to be dense. All the PEGs increased the permeability and antifouling properties of CPVC/PVB blended membranes remarkably. Among them PEG 4000 and PEG 6000 increased much more. However, the retention and mechanical property declined a little. PEG 6000 as an additive could make CPVC/PVB blended membranes have better membrane properties.
    Progress on the production of 1,3-propanediol by fermentation
    LI Xiaoshu, ZHANG Lin, GAO Dacheng, SHI Wenjing, FAN Yachao
    2017, 36(04):  1395-1403.  doi:10.16085/j.issn.1000-6613.2017.04.032
    Abstract ( 1061 )   PDF (474KB) ( 1030 )  
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    1,3-propanediol is an important chemical compound,which has recently received more and more attention due to its wide applications. Synthesizing 1,3-propanediol via the biological method has some merits,such as green,high efficiency,and sustainable. This method is the most promising for the 1,3-propanediol production.In this paper,the research advances on production of 1,3-propanediol by fermentation were reviewed with regard to fermentative strains,fermentation process,process optimization and purification. To have a low cost advantage over the other chemical synthesizes,the biological method needs to increase the concentration of 1,3-propanediol,to strengthen the fermentation process that is more accurate and easier control. Economy and energy consumption need to be considered to integrate the whole process of fermentation and separation,which should be the focus of research and industrial production of 1,3-propanediol by biological process in the future.
    Research progress on cell immobilization technology in ethanol production
    ZHANG Qiang, JI Ye
    2017, 36(04):  1404-1409.  doi:10.16085/j.issn.1000-6613.2017.04.033
    Abstract ( 328 )   PDF (452KB) ( 640 )  
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    Cell immobilization technology was developed in 1970's based on the enzyme immobilization. Recently,cell immobilization is widely used in research and production of fuel ethanol. It demonstrated great potential with advantages of repeated applications,continuous operations,and high ethanol yield. So researches on cell immobilization in ethanol production are very important for practical applications. This article reviewed research progresses on cell immobilization in ethanol production. The article discussed the common methods,characteristics and advantages and applications of cell immobilization,problems,and solutions. The keys for future ethanol productions are developing co-immobilization of cell-cell,cell-enzyme and self-immobilization cell technologies, and developing new immobilization support materials for ethanol production.
    Cell transporter protein and engineered applications
    YANG Kun, WANG Ying, LI Chun
    2017, 36(04):  1410-1417.  doi:10.16085/j.issn.1000-6613.2017.04.034
    Abstract ( 362 )   PDF (812KB) ( 468 )  
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    There are a lot of cell transport proteins. They play an important role in many physiological activities,such as uptaking nutrients,releasing metabolites,and transducting signal processes on biofilms. According to the transporting way of the cell transport proteins,they can be devided into channel protein,carrier protein,and ATP-powered pump. ABC transporters(ATP-binding cassette transporters),which is a kind of cell transporter proteins widely distributed in organisms,can transport a variety of compounds with energy supplied by ATP hydrolysis. In recent years,it has drawn widely attention regarding the multi-drugs resistance of animal cells and the self-defense of plants under external stress. The understanding of the cellular transport proteins provides the basis for effectively using it. This paper illustrated the structures and mechanisms of ABC transporter proteins found in plants,animals,and microbial cells;and summarized the progress of engineering applications of cell transporter proteins in various fields and the remaining problems. Finally,guidance will be provides to use cell transporter proteins in developing cancer drug,improving crop yield as well as efficient synthesis of metabolites in engineered microorganisms.
    The continuous butanol fermentation of symbiotic system TSH06
    LI Dongyue, LI Xianglong, LIN Zhangnan, LIU Hongjuan, ZHANG Jian'an
    2017, 36(04):  1418-1423.  doi:10.16085/j.issn.1000-6613.2017.04.035
    Abstract ( 277 )   PDF (748KB) ( 573 )  
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    The traditional butanol producing strain was strict anaerobic bacteria. A facultative anaerobic symbiotic system TSH06 was isolated in our lab,which could produce butanol under micro-aerobic conditions. This work studied the continuous butanol fermentation of TSH06 under the micro-aerobic condition. The effect of dilution rate on the cell growth and butanol production was investigeted. The test results indicated that the lower dilution rate enhanced the butanol production and the higher dilution rate was beneficial for the acid accumulation. However,the butanol productivity decreased when the dilution rate was higher than 0.2h-1. The optimized dilution rate was 0.2h-1 with the butanol productivity of 1.06 g/(L·h). The results provided the theoretical basis for the further optimization of butanol continuous fermentation under micro-aerobic conditions.
    Research progress in preparation of ε-caprolactone by cyclohexanone green oxidation
    YAN Jie, ZHAO Lihong, SONG Can, JIANG Yuanli, WEI Lingchao
    2017, 36(04):  1424-1428.  doi:10.16085/j.issn.1000-6613.2017.04.036
    Abstract ( 368 )   PDF (408KB) ( 624 )  
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    ε-caprolactone is a new kind of polyester monomer. Polyester made from it possess excellent biocompatibility and biodegradability and is used in many fields such as biomedical engineering and biodegradable plastics. Green oxidation cyclohexanone to caprolactone is a research hot topic for preparation of ε-caprolactone. The recent laboratory investigation progress in cyclohexanone green oxidation was reviewed from the aspects of cooxidation and in-cooxidation with oxygen and hydrogen peroxide as oxidizing agents. The merit and demerit were introduced based on the catalyst and coproducts treatment,and the development status and tendency of its industrialization were analyzed. The method of in-cooxidation with hydrogen peroxide is the most economical and of development potential at present,but the key points are the efficient and stable catalyst as well as efficient dehydration technology for the reaction. The cycle route of the coproduction in cooxidation with oxygen was prospected,which should be the optimal way of production ε-caprolactone.
    Sunscreen ingredients of synotis erythopappa(Bur. et Franch)C. Jeffey et Y. L. Chen and its application in sun cream
    XU Chuntao, MA Fei, JI Hongbing
    2017, 36(04):  1429-1433.  doi:10.16085/j.issn.1000-6613.2017.04.037
    Abstract ( 269 )   PDF (542KB) ( 209 )  
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    Synotis erythopappa(Bur. et Franch) C. Jeffeyet Y. L. Chen,as an endemic compositae in Tibete,has potential benifits in whitening and sun blocking. In this paper,four different solvents(water,hexane,aether and alcohol) were used to extract the plant,respectively. The extraction was investigated by testing actual UV absorbtion value. Using the best extract solvent,different extract technologies were used to evaluate the effectiveness of the extraction. The results showed thatethanol,as the extract solvent and combing with ultrasonic extraction technology,the exctraction rate was up to 27%. Gas chromatographymass spectrometer(GC-MS) was used to analyze the sun block components from extract solvent. It was found that 3-methylene-6-(1-methyl ethyl) cyclohexene,cyclohexene,pinene,myrcene,with conjugated double bonds could absorb ultraviolet. With the synotis erythopappa(Bur. et Franch)C. Jeffey et Y. L. Chen extract as a sunscreen ingredient,it was found sunscreen with 2.5% mass fraction of synotis erythopappa(Bur. et Franch) C. Jeffey et Y.L.Chen had very good UV protection in UVB(290-320nm) ultraviolet region,and the average absorbance value was 1.95.
    Research progress in treatment technology for exhaust gas from spray paint process
    SHENG Nan, WEI Zhouhaosheng, CHEN Minggong, SUN Yimei, HAN Xiao
    2017, 36(04):  1434-1447.  doi:10.16085/j.issn.1000-6613.2017.04.038
    Abstract ( 394 )   PDF (670KB) ( 1310 )  
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    Spraying coating has been extensively applied in the chemical engineering,automobile and ship industries. In the application process,the exhaust gas from spray paint process brought negative influences on environment and human health. This paper introduces the major components and damage of exhaust gas from spray paint process,comprehensively illustrates the purification techniques in waste gas from spraying and analyzes the pre-processing techniques of paint mists as well as the purification techniques in processing VOCs of the organic waste gas. Among them,paint mist pre-processing is mainly divided intro wet processing method and dry processing method. VOCs purification techniques including traditional purification processing techniques,such as adsorption method,absorption method,combustion method and condensation method. The new type purification processing techniques,for example,separation membrane method,photocatalysis method,bioanalysis method,plasma cleaning method and compound purification processing techniques was included. It explains the strengths and weakness of purification mechanism and process procedures,proposing that the compound-type purification processing technique is the development direction in processing exhaust gas from spray paint process in the future. Meanwhile,it points out that the running cost,operating difficulty and stability serve as the urgent problems which shall be solved for the compound-type processing techniques.
    Research progress on hydrogen and sulfur production from direct decomposition of hydrogen sulfide
    ZHANG Jing, ZHANG Tie, SUN Feng, XU Wei, SHI Ning
    2017, 36(04):  1448-1459.  doi:10.16085/j.issn.1000-6613.2017.04.039
    Abstract ( 392 )   PDF (571KB) ( 718 )  
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    Direct decomposition of hydrogen sulfide is an effective way not only to treat the waste gas in coal,petroleum,natural gas and mineral processing industries for solving the environmental pollution problems but also to produce sulfur and a clean energy,hydrogen. In this paper,the research progress of hydrogen and sulfur produced from direct decomposition of hydrogen sulfide including themolysis(directly high-temperature thermolysis,catalytic thermolysis and superadiabatic thermolysis),electrochemical technology,photocatalytic decomposition and plasma technology are reviewed. Fundamental principle and themodynamic basis of methods involved are briefly introduced. Then, a detailed description of research status focused on research methods,technique feature,reaction performance,advantage and disadvantage,and potential breakthrough point,etc. is given. The future development trend is prospected at the end of this review as well. A prospect is put forward that continuously exploring and developting new technologies such as combining membrane technology,catalytic technology and plasma technology would be the future trend in the field of hydrogen production from H2S decomposition.
    Research progress on selenium removal of FGD wastewater from coal-fired power plants
    ZHANG Shenghan, SUN Chenhao, CHEN Yuqiang
    2017, 36(04):  1460-1469.  doi:10.16085/j.issn.1000-6613.2017.04.040
    Abstract ( 350 )   PDF (698KB) ( 833 )  
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    The wastewater resulting from wet flue gas desulfurization(FGD) in coal-fired power plants enriches selenium which will destroy the surrounding environment and cause the endemic diseases. This paper provided an overview of existing technologies of selenium removal and their application in FGD wastewater treatment field,summarized advantages and disadvantages of each technology,and also pointed out their application prospects. The related literatures,patents and cases of each method were counted briefly. The effective methods(chemical reduction,membrane separation process,biological process,coagulation process,ion exchange resin and adsorption) were mentioned respectively. The pH and co-existing anions in aqueous solution appeared to have a significant impact on removal efficiency. The coagulation and biological combined processes were proved to be the most applicative technology by analysis and comparison. The lack of emission standard and technology research of selenium in FGD wastewater were the current characteristics of the domestic coal-fired industry. Considering the cost and operation,coagulation process may be the most economical and feasible method of selenium removal for the domestic situation in the near future.
    Removal of organic chlorine in simulated oil by adsorption
    LI Ruili, LI Jingjing, ZHANG Ping
    2017, 36(04):  1470-1475.  doi:10.16085/j.issn.1000-6613.2017.04.041
    Abstract ( 359 )   PDF (667KB) ( 642 )  
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    Removal of organic chloride in oil was studied by direct adsorption. MgO/ZSM-5,CuO/ZSM-5,CuO/γ-Al2O3 and MgO/γ-Al2O3 adsorbents were prepared by saturated impregnation with ZSM-5 zeolite and γ-Al2O3 as carrier,CuO and MgO as the active ingredient. The structures of adsorbents were characterized by BET and XRD. Dechlorination performance of the obtained adsorbents was studied in simulated oil. Meanwhile,reaction conditions of the dechlorination experiments were studied on chlorinated organic removal effect. Then, the optimum adsorption conditions were obtained. Experimental results have shown that the effects of dechlorination of MgO/ZSM-5 and CuO/ZSM-5 were better than others and the optimal adsorption conditions were as follows:the loading amount of active ingredient was 12%(w),adsorption temperature was 30℃,the ratio of catalyst to oil was 1:15,the adsorption time was 60min,the dechlorination rate were 62.63% and 56.28% respectively. Finally,the adsorption of single organic chlorides in simulated oil was studied. The adsorbents had different removal effects for the different concentrations of chlorinated organics, which provided experiences and basis for removal of different organic chlorides in naphtha.
    Cr speciation and hazardous waste identification in tannery sludge
    ZHOU Jianjun, MA Hongrui, ZHU Chao, WU Wei, CAO Ling, SUN Wenyue
    2017, 36(04):  1476-1481.  doi:10.16085/j.issn.1000-6613.2017.04.042
    Abstract ( 282 )   PDF (519KB) ( 253 )  
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    To reveal the correlational relationship between tannery sludge hazardous waste identification and the ecological risk and speciation of Cr,this paper investigated component analysis and the leaching toxicity and speciation of Cr in tannery sludge,and removal of Cr from tannery sludge by hydrochloric acid was also performed. Results showed that tannery sludge is a typical industrial solid waste with a great amount of organic matter and inorganic salts,as well as a variety of metallic elements in dominated by Ca,Fe,Cr,Al and Cr which is of the highest harm to the environment. The acidly soluble and organic matter bonding fractions are the main speciation of Cr in tannery sludge,while the bioavailability of Cr only accounted for a smaller proportion in amount,nevertheless its mobility under acidic condition still may result in a high ecological risk. In this study,the leaching concentration of Cr was lower than 0.25mg/L,showing no leaching toxicity,but the environmental behavior of Cr still makes it hazardous waste. The extraction efficiency of Cr was up to 81.7% by hydrochloric acid and acceptable for reutilization,indicating hydrochloric acid was suitable for Cr extraction in tannery sludge.
    Reaction mechanism on autoclaved aerated concrete made from low-grade vanadium titanium iron tailings
    LUO Liqun, SHU Wei, CHENG Qilin, TAN Xusheng
    2017, 36(04):  1482-1490.  doi:10.16085/j.issn.1000-6613.2017.04.043
    Abstract ( 288 )   PDF (3936KB) ( 760 )  
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    Based on low-lean vanadium and titanium iron tailings as raw material,the technology of autoclaved aerated concrete(AAC) block was developed,in which compressive strength was more than 3.5MPa and dry bulk density prepared was about 620kg/m3. The products was slightly more than A3.5B06 grade qualification requirements. The physical and mechanical properties,the vibration of the functional group,phase transformation process,microstructure,etc. of aerated concrete block were tested by X-ray diffraction(XRD),fourier transform infrared spectroscopy(FTIR),thermogravimetric and differential scanning calorimeter(TG-DSC),scanning electron microscope(SEM) and other modern analysis test methods. Under the atmospheric pressure,the iron tailings was a kind of inertia industrial waste residue. Only a small amount of active component in iron tailings participated in the chemical reaction. Small amounts of the hydrated calcium silicategel and ettringite were in the hardened body. Under the autoclaved curing condition,the activity of iron tailings was good. Free SiO2and Al2O3 and mixture of Ca(OH)2 took place chemical reaction to generate tobermorite. A dense mesh structure was formed by hydration products of crystal cluster fitting aggregating together,which had positive effect to improve the strength of the products.
    Synthesis of ESA-polymers containing sulfonic acid groups and their performance comparison
    LI Haihua, GAO Meiling, ZHANG Lihui, GAO Yuhua, LIU Zhenfa
    2017, 36(04):  1491-1498.  doi:10.16085/j.issn.1000-6613.2017.04.044
    Abstract ( 344 )   PDF (2721KB) ( 315 )  
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    Four ESA-polymers containing sulfonic acid groups were synthesized by copolymerization of monomers of epoxysuccinic acid(ESA) and sodium allyl sulfonate(SAS),sodium styrene sulfonate(SS),2-acrylamido-2-methylpropanesulfonic acid(AMPS) and itaconic acid(IA). Their molecule structures were characterized by FTIR spectrum,and the crystalline shapes of the CaCO3 formed from different polymers were observed by SEM. The scale inhibition and dispersion performances of the polymers were studied and compared with those of PESA. The results showed that the polymer of ESA/IA/AMPS had comprehensive water treatment performances,which showed excellent scale inhibition performances to CaCO3 and Ca3(PO4)2 in the water of high hardness and alkalinity. When the dosage was 40mg/L,the inhibition rate to CaCO3 scales was 82.7%,10.4% higher than that of PESA. When the dosage was 30mg/L,the scale inhibition rate to Ca3(PO4)2reached 100%. Moreover,ESA/IA/AMPS was easy to be biodegraded,and its biodegradation percentage reached 72.7% after 14d.The results of SEM showed that there were vaterite type CaCO3in the scales formed in the water samples with the addition of the polymers. This indicated that the polymers could stabilize the unstable phase,and thus enhance the solubility and dispersion of CaCO3 in water.
    The preparation of biochar from pre-oxidation of banana stem and its adsorption of Cu2+
    YU Weiguang, LI Jihui, WANG Dun, LIANG Zhenyi, ZHANG Yucang
    2017, 36(04):  1499-1505.  doi:10.16085/j.issn.1000-6613.2017.04.045
    Abstract ( 312 )   PDF (2294KB) ( 524 )  
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    A novel approach was used to prepare engineered biochar from banana stem pretreated with KMnO4 through slow pyrolysis(600℃). The physicochemical properties of biochar were characterized. Batch adsorption experiments were conducted to investigate the effect of pH values,contact time,temperature and initial Cu2+ concentration on the adsorption efficiency and behaviors. The adsorption types were analyzed from the aspects of kinetic,isotherms,and thermodynamic. The results showed that the engineered biochar surface was covered with MnOx ultrafine particles. In comparison to the pristine biochar,the engineered biochar had more surface oxygen-containing functional groups and much larger surface area. The removal of the metals by the engineered biochar was mainly through surface adsorption mechanisms involving both the surface MnOx particles and oxygen-containing groups. The biochar had strong adsorption ability to Cu2+ with maximum adsorption capacities of 81.36mg/g in experiments,which was significantly higher than that of the pristine biochar. The adsorption process was consistent with the pseudo-second-order model. The process was better described by the Langmuir isotherm model. ΔG0 was negative and ΔH0 was positive,indicating spontaneous and endothermic adsorption.
    Effect of toluene on the EPS in the microorganisms of biotrickling filter
    JIA Yanping, JIANG Cheng, ZHANG Lanhe, ZHANG Haifeng, CHEN Zicheng
    2017, 36(04):  1506-1511.  doi:10.16085/j.issn.1000-6613.2017.04.046
    Abstract ( 292 )   PDF (749KB) ( 244 )  
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    Volatile organic compounds(VOCs) have the characteristics of wide sources,numerous varieties,and tremendous hazardous. To improve the removal efficiency of VOCs,an extensive toluene treatment experiment was continuously conducted using biotrickling filter. The effect of toluene inlet concentration on the removal efficiency and extra-cellular polymeric substance(EPS) of biofilm in the biotrickling filter were investigated. The results showed that the removal efficiency of toluene was higher than 95%,and the EPS was 339mg/L when the inlet concentration of toluene and the spray volume were 284mg/m3 and 3.7-6.3L/h,respectively. With the increase of inlet concentration,the protein concentrations and polysaccharide in the loosely bond extra-cellular polymeric substances (EPS-LB) increased to a peak values of 108.93mg/L and 103.95 mg/L,respectively before they dropped. The change of protein and polysaccharide concentration in the tightly bond extra-cellular polymeric substances(EPS-TB) was similar to that of EPS-LB. It was not conducive to remove toluene in the biotrickling filter when the spray water volume was less than 3L/h or more than 7L/h. Pressure drops increased with the increase of inlet flow and EPS,and they were significantly higher at the end of experiment than those at the beginning of the experiment. However,the pressure drops of the biotrickling filter were remaining at low value.
    Effect of exogenous absorbents addition on CO2 absorption performance of biogas slurry and its agricultural application
    WANG Wenchao, HE Qingyao, YU Ge, LIU Lu, YAN Shuiping
    2017, 36(04):  1512-1520.  doi:10.16085/j.issn.1000-6613.2017.04.047
    Abstract ( 278 )   PDF (660KB) ( 708 )  
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    Biogas slurry is the byproduct of biogas produced by anaerobic fermentation of biomass,which is weak alkaline and rich in useful ingredients stimulating the plant growth. Theoretically,biogas slurry can be used as a renewable absorbent combining CO2 absorption and CO2 biological fixation. But CO2 absorption performance of biogas slurry needs to be enhanced. Adding exogenous CO2 absorbents into biogas slurry can contribute to promoting CO2 absorption performance of biogas slurry,but also affect its phytotoxicity. So,the effects of 6 exogenous CO2 absorbents added into biogas slurry on CO2 absorption performance of biogas slurry were investigated using the typical CO2 bubbling absorption system. Additionally,the feasibility of agricultural application of CO2-rich biogas slurry was also explored in terms of the change of phytotoxicity and total phosphorus concentration before and after adding exogenous CO2 absorbents. The results showed that ammonia nitrogen,the main harmful substance in the biogas slurry,could be removed by concentrating biogas slurry at vacuum conditions. And the removal efficiency of ammonia nitrogen could reach up to about 87.69% when the biogas slurry concentration was increased by 5 times. Compared with adding absorbents into the raw biogas slurry directly,adding the same absorbents with high concentrations into the concentrated biogas slurry could greatly improve the CO2absorption capacity. In addition,when the concentrated CO2-rich biogas slurry was diluted so that the concentration of CO2 absorbent concentration was equal to that of the raw biogas slurry,the germination index(GI) of Chinese cabbage treated by the concentrated CO2-rich slurry was higher than that treated by raw biogas slurry. Moreover,adding exogenous absorbents in biogas slurry can help remove the total phosphorus in biogas slurry,which reduces the environmental hazards for agricultural applications. Among all of 6 exogenous absorbents,MEA has the comprehensive advantages in terms of improving CO2 absorption performance and reducing the phytotoxicity of biogas slurry.
    Thermal performance comparison of flash-binary power system
    LUO Ke, LUO Chao, GONG Yulie
    2017, 36(04):  1521-1528.  doi:10.16085/j.issn.1000-6613.2017.04.048
    Abstract ( 309 )   PDF (848KB) ( 747 )  
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    To select a suitable working fluid for flash-binary power system(FBPS),a thermodynamic model for FBPS was established. In this calculation,the heat source temperature of the FBPS is 100-150℃ with a flow rate of 36t/h and cooling water inlet temperature is 15℃. Five organic working fluids(R236fa、R600a、R600、R245fa、R601a) were selected to analyze their work capacity based on the performance index of net power output per ton of geofluid,thermal efficiency,exergy efficiency and irreversible loss of the system. Finally,the best working fluid was determined. Results showed that the net power output of FBPS increases with the increase of flash temperature and then decreases. Each working fluid has an optimum flash temperature which makes the net power output to be maximum. Taking environmental and thermodynamic performance into consideration,R245fa is the best working fluid for the flash-binary power system.
    A serial-parallel combined connection pattern for indirect heat integration among three plants based on maximum heat recovery
    SONG Runrun, WANG Yufei, FENG Xiao
    2017, 36(04):  1529-1533.  doi:10.16085/j.issn.1000-6613.2017.04.049
    Abstract ( 230 )   PDF (656KB) ( 353 )  
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    More opportunity to utilize the waste heat in several plants can be brought by indirect interplant heat integration through an intermediate medium. The connection patterns of intermediate medium circles concern the maximum heat recovery potential and investment costs. The three basic connection patterns of intermediate medium circles are serial,split,and parallel,respectively. Based on these patterns,a serial-parallel combined connection pattern was presented in this paper. Furthermore,the interplant shifted composite curves and intermediate medium curves of this pattern were also illustrated. Results of a case study showed that,the serial-parallel combined connection pattern can recover more heat than the serial and spilt patterns. Its maximum heat recovery potential even approaches to that of the parallel pattern,which can always recover the most heat among the three basic connection patterns. The pipe costs of intermediate medium circles vary with the distances between plants. A proper connection pattern should be selected according to the characteristics of distances between plants.
    Review of risk assessment and pre-control of Domino effect in Chemical Industry Park
    JIA Meisheng, CHEN Guohua, HU Kun
    2017, 36(04):  1534-1543.  doi:10.16085/j.issn.1000-6613.2017.04.050
    Abstract ( 501 )   PDF (487KB) ( 970 )  
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    Quantitative risk assessment of Domino effects(DMQRA) is the key method to be used to prevent Domino accidents in chemical plants or parks. Also,the various pre-control measures and their availability evaluations are based on the result of DMQRA. However,there are many inconsistent or unclear interpreted modes and methods for presentation of probability risk,probability structure of Domino scenarios and damage probabilities of target equipment exposed to fire or blast such that the obtained DMQRA results are in a great variability. Moreover,it is hard to evaluate the specific pre-control measures. In this paper,firstly,the concept and basic principles of Domino effect are clearly defined. Then through carefully analyzing of the various DMQRA methods in literature,the probability structure of Domino scenario and damage probabilities of target equipment attacked by fire thermal radiation,blast wave overpressure and blast fragments are outlined clearly. In addition,damage thresholds,safety distances,safety inventories,layout optimization,safety barriers,thermal insulations,decision supporting for safety and emergency management,security,resilience and natural hazards triggering for domino effect are reviewed in detail. Finally,it is figured out that the advanced methods for calculating of damage probabilities of target equipment exposed to fire,blast and other triggering vectors,i.e. equipment vulnerability,will be focused upon in the future.
    Construction of intelligent emergency rescue platform for Chemical Industry Park
    KANG Deli, LIU Limin, JI Hongbing
    2017, 36(04):  1544-1549.  doi:10.16085/j.issn.1000-6613.2017.04.051
    Abstract ( 309 )   PDF (813KB) ( 412 )  
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    Chemical Industry Parks are growing rapidly in recent years,but also are suffering from the increasing risk of accident. In this paper,the complexity and the degree of difficulty of emergency rescue management in the Chemical Industry Park were analyzed and it was found that the building intelligent emergency rescue platform could effectively improve the efficiency and accuracy of emergency rescue actions. The framework of the intelligent emergency rescue platform consisted of two parts:the sensor network for collecting data and the data processing based on field information for giving advices to commander. The four key points of intelligent emergency rescue platform including data acquisition,data analysis,communication and execution were presented. The role of information in the process of emergency rescue should be highlighted. Information as a resource had a significant contribution to emergency rescue similar with emergency equipment. The intelligent emergency rescue platform realized the efficient selection,accurate analysis and rapid transfer of information in the process of emergency,aiming to help decision-makers to make decisions quickly and properly by providing efficient,intelligent and intuitive knowledge. Due to the rapid and accurate access to the field of information,it played an important role in promoting accurate emergency.
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