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Table of Content
05 May 2012, Volume 31 Issue 05
    Research and application progress of the catalytic synthesis of environmental plasticizers
    JIANG Pingping,ZHANG Shuyuan,LENG Yan,DONG Yuming,ZHANG Pingbo
    2012, 31(05):  953-964. 
    Abstract ( 1693 )  
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    New methods of catalytic synthesis of novel plasticizer,catalytic reaction process,catalyst type and preparation were summarized. Properties of major domestic and overseas new environmental protection plasticizers,applications and the research status were especially focused on,including the synthesis and properties of biological-base vegetable oil plasticizer,polyester plasticizer,citric acid ester plasticizer,trioctyl trimellitate plasticizer and dioctyl terephthalate plasticizer. At the meantime,compared with the traditional synthesis method and catalyst,the trend of catalytic synthesis of plasticizer and the application direction of plasticizers in national high-tech fields were pointed out. Put forward the plasticizer industry and new materials additive field in our country development should focus on the adjustment of product structure, accelerate the exploitation of non adjacent benzene structure, plant oil base plasticizer.
    Research progress of heat transfer enhancement in two-phase closed thermosyphon
    WANG Xinyu,XIN Gongming,TIAN Fuzhong,QU Fulong,CHENG Lin
    2012, 31(05):  965-973. 
    Abstract ( 1609 )  
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    This paper reviewed the current research of heat transfer enhancement technologies on the two-phase closed thermosyphon. Heat transfer enhancement technologies were classified into highly efficient working fluid application,inner surface treatment,pipe inserted into the thermosyphon,and other methods. The heat transfer enhancement mechanism of these technologies was analyzed. The result indicates that most technologies stay in the experimental level and lack the theoretical research. And they have not obtained any widespread industrial application yet. Theoretical study,research of the effect of parameters on the heat transfer performance,how to reduce the production costs of industrial application will be the hot research topics of heat transfer enhancement technologies with thermosyphon in the future.
    Impact of the characteristics of adsorbents on the adsorption and separation of CO2/CH4 binary system
    LI Yundong,YI Honghong,TANG Xiaolong,LI Fenrong,HE Dan
    2012, 31(05):  974-980. 
    Abstract ( 1773 )  
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    There are many types of adsorbents which are used for adsorption and separation of CO2/CH4 binary mixtures system. It is the various characteristics of adsorbents that affect separation result. As a starting point,four kinds of adsorbent properties affecting separation,which include porous structure,exchangeable cations,surface chemistry and moisture of adsorbent,are summarized in this article and the reason of all kinds of influences are explained. We come to several conclusions,including that mesoporous is conducive to the separation and amine grafting;the introduction of corresponding exchangeable cations can enhance the affinity between quadrupole and adsorbents,and improve the adsorption selectivity;surface hydroxyl is also an important factor affecting grafting amine;moisture can enhance the separation performance of adsorbent but also is conducive to grafting amine.
    Numerical simulation of a single droplet freezing process
    GENG Xianru,XU Qing,LI Zhanyong,SONG Jitian
    2012, 31(05):  981-986. 
    Abstract ( 1594 )  
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    Droplets freezing process by spray freezing leads to their complex microstructures due to the formation of ice crystals within droplets. Numerical simulation was conducted to study the effect of droplet size,gas velocity and environmental temperature on the freezing process for a single droplet. Uniform temperature model was adopted in the simulation of droplet freezing process. The results show that the total solidification time for larger droplet is about 3 orders longer than that for the smaller one. Freezing rate is enhanced as gas velocity increases and environmental temperature decreases. Using variance analysis method,it is found that droplet size,gas velocity and environmental temperature have significant impacts on droplet total solidification time(p=0.0063>0.05). During cooling process,the ratio of droplet mass loss due to convection decreases to lesser extent with the increases of droplet size and gas velocity,which is about 2%. Lower environmental temperature,which is an influential parameter,results in lower droplet mass loss ratio.
    Influent of optimization order of heat exchanger on the global optimization result of heat exchanger networks
    HU Xiangbai,CUI Guomin,XU Haizhu,HE Qiaole
    2012, 31(05):  987-991. 
    Abstract ( 1438 )  
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    In order to overcome the difficulty of being easily trapped in local optimal solution during the global optimization process of heat exchanger network,the Monte-Carlo random sampling technique was applied to the random combination of cold fluid and hot fluid in the heat exchanger network. Through this way,the random changes of optimization sequence about multi-dimensional parameters were accomplished,the global optimal result of heat exchanger network could be sought out during jumping out from one local minimum solution to another. Through a case study,compared with previous results,the better result was obtained using this optimization method which is more suitable to industrial applications.
    Tri-temperature control method on cyclic total reflux batch distillation without reflux drum
    HUANG Lili,BAI Peng,WANG Lei,YIN Kun,JIANG Zhankun
    2012, 31(05):  992-996. 
    Abstract ( 1376 )  
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    A control method of total reflux by introducing temperatures of top part,upper-middle part and middle part in batch distillation column without reflux drum was proposed. The ethanol—n-propanol system identified as a typical ideal system was used to conduct the experimental study of this operation. The optimized temperature control conditions were determined by experiments:when the temperature of the top part was stable and difference between the upper-middle part and the top part was 0.3 ℃,the total reflux operation would be switched to the total withdrawal operation,and if the temperature of the middle part rose by 1 ℃,the total withdrawal operation should be converted to the total reflux operation. From the results of experiments under the same operating conditions,the influence of different feed concentrations on the overhead product average purity is not significant,basically maintained at 0.99(mass fraction). Finally,compared with dual temperature control method under the same feed concentration and operating conditions,this tri-temperature control method reduces operating time by 23.3 min,promotes separation efficiency by 23.95%,increases the purity of product by 1.06% and increases the product yield by 1.08%.
    Study on the configuration of internal thermally coupled reactive distillation column
    LI Jun1,2,SUN Lanyi1,ZHOU Xiantian1,WANG Rujun1,HU Yangdong1
    2012, 31(05):  997-1003. 
    Abstract ( 1541 )  
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    The model for applying an internal thermally coupled reactive distillation column(ITCRDC)to hydrolysis of methyl acetate was studied by using the simulation software,Aspen Plus. On the premise of ensuring the purity of products and minimum approach temperature,the effects of the various configurations of ITCRDC on the energy saving were explored. The results suggested that configuration had great influence on the performance of ITCRDC for the hydrolysis reaction of methyl acetate and the optimal one was obtained. And the characteristic of the optimal configuration is that the reaction section is in the rectifying tower and the stripping tower is thermally coupled with the rectifying tower.
    Steady state simulation of fluidized catalytic cracking(FCC)unit:Effects of regenerator heat remover duty on the process
    LI Guotao1,SUI Hong1,2,WANG Hanming3,XU Changchun1,2,LI Xin1,LI Guangbin2,LI Xingang1,2
    2012, 31(05):  1004-1009. 
    Abstract ( 1299 )  
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    Steady state simulation research was carried out for one industrial fluidized catalytic cracking(FCC)unit using the simulation platform developed by our group. The unit model was calibrated and validated by the industrial data collected from the unit. The effects of regenerator heat remover duty on the unit operation were then simulated and analyzed in this paper. The simulation results showed that,via the regulation of regenerator heat remover duty,the unit operator could change unit heat balance effectively and tune up the ratio of catalyst to oil before violating the operating range of process variables,thus more feedstocks could be converted to lighter products and the products distribution could then be adjusted effectively. However it could also decrease the temperature of dense bed in second stage regenerator and then deteriorate the operating performance of regenerator,thus its application is not conducive to improve the initial activity of regenerated catalyst.
    Advances in H2 production from the aqueous-phase reforming of biomass-derived polyols:A review
    JIANG Tao,CHEN Shishi,CAO Fahai
    2012, 31(05):  1010-1017. 
    Abstract ( 1552 )  
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    Aqueous-phase reforming of biomass-derived polyols is one of the ongoing and promising technologies for hydrogen production. In this paper,the recent advance in hydrogen production by aqueous-phase reforming of biomass-derived polyols is reviewed. First,the thermodynamic and kinetic considerations that form the basis of the process are discussed. Then,the reaction pathways and the catalytic system as well as the optimization of technological conditions are introduced. In comparison with the process of steam reforming,the advantages and disadvantages of aqueous-phase reforming are proposed. On the one hand,the technology of aqueous-phase reforming possesses the features of lower energy consumption,less processing steps and relatively simple post-processing. On the other hand,there are more side reactions and the yield of H2 is lower. Finally,the review points out that the research directions are the development of more effective and stable catalysts,and the reduction of the cost for catalysts preparation and the optimization of the processing condition in the future.
    Mechanisms of carbon deposit formation and removing in internal gasoline engines and research progress of gasoline detergent additives
    LU Xiang,SITU Yue,XIE Delong,HUANG Hong
    2012, 31(05):  1018-1022. 
    Abstract ( 1747 )  
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    During the lifetime of an internal engine,carbon deposit forms at various locations,such as combustion chamber,injection nozzle and inlet valve. Engine carbon deposit has serious influences on the engine efficiency,driveability and exhaust emissions. In order to clean up the carbon deposit,gasoline additives have become a necessary part of modern engine fuel. A large number of research literatures suggest that carbon deposit formation has two steps,i.e. initiation and growth;and these processes would be affected by metal surface temperature,fuel composition,injection rate,and many other factors. The use of a particular structure of the organic amines which can be adsorbed on metal surfaces and disperse pectin can clean the extensive carbon deposit. In addition,the composition,the development and the evaluation method of gasoline detergent have been summarized.
    Optimization for the hydrocracking process of the heavy fraction of medium temperature coal tar
    LI Bin, LI Dong,LI Wenhong,CUI Louwei,LEI Yuchen,WANG Junce,LIU Cunju,LI Hong
    2012, 31(05):  1023-1027. 
    Abstract ( 1544 )  
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    Analysis and optimization of hydrocracking process conditions for the heavy fraction of medium temperature coal tar in a fixed-bed hydrogenation unit was investigated using single-factor tests and response surface methodology. The optimized process condition was found as:reaction pressure of 13.4 MPa,reaction temperature of 682 K,hydrogen to oil volume ratio of 1895?1 and liquid hourly space velocity of 0.30 h?1,under which the conversion rate of the heavy fraction of coal tar hydrogenation was 77%—78%.
    Research on the preparation of ethylene from bio-ethanol
    JIA Baoying,DU Ping,DU Fengguang,SUN Peiyong,NIU Delong
    2012, 31(05):  1028-1031. 
    Abstract ( 2265 )  
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    The increasing of crude oil price and the development of bio-ethanol have influenced ethylene industry. It is a good chance for the development of technology of ethylene from ethanol dehydration. The processing conditions for preparing ethylene with HZSM-5 from aqueous bio-ethanol were researched. The factors which influence the conversion ratio of ethanol and the selectivity of ethylene,such as reaction temperature,the mass concentration of aqueous ethanol and weight hourly space velocity(WHSV)were studied. After a series of experiments,the optimal condition was determined as follows:the reaction temperature of 230 ℃,WHSV of 1.5 h-1 to 1.7 h-1,the mass concentration of ethanol of 80g/L to 150g/L. The conversion ratio of ethanol is more than 99%,and the selectivity of ethylene is over 98%.
    Supported metallocene onto multi-morphological mesoporous materials for polymerization of ethylene
    KANG Yu,ZHANG Mingsen,WANG Hongtao,XIE Lunjia,JIANG Jianzhun,
    2012, 31(05):  1032-1038. 
    Abstract ( 1360 )  
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    Four kinds of catalysts have been prepared by supported(n-BuCp)2ZrCl2 and MAO onto the mesoporous materials with different morphologies including rod-like,sphere-like,doughnut-like and hollow sphere-like shapes firstly and successfully. The structure and morphology of the catalysts have been studied. And the catalysts have been investigated for the polymerization of ethylene. The result of ethylene homopolymerization and ethylene/1-hexene copolymerization catalyzed by metallocene adduct catalyst confirmed that catalyst possessed higher activity in copolymerization and homopolymerization than 955 silica gel,and that hollow sphere-like catalyst is the most suitable carrier for ethylene polymerization .
    Preparation of Cu-BiVO4 photocatalyst and its application in the treatment of phenol-containing wastewater
    GAO Xiaoming1,2,FU Feng1,Lü Lei1,WU Yufei1,WANG Jing1,LI Wenhong2
    2012, 31(05):  1039-1042. 
    Abstract ( 1695 )  
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    Cu metal modified BiVO4 was prepared by hydrothermal method,which was investigated by photocatalytic oxidation of phenol-containing wastewater. The effects of pH of catalysts prepared and photocatalytic reaction techniques on the removal performance of phenol were studied. The results showed that the degradation rate of Cu-BiVO4 to phenol in wastewater was up to 92.4%,under the condition as,7 of pH catalysts prepared,1 mg/L of catalyst dosage,200 mL/min of air flow,illumination 3 h. The composite photocatalysts were characterized by X-ray diffraction and ultraviolet-visible absorption spectroscopy. The Cu-BiVO4 catalyst has a significant red-shift in the absorption band in visible region,and the absorption intensity increases greatly for the composite catalyst.
    Study on the performance of photocatalytic degradation of phenol using cerium doped nano-TiO2 under visible irradiation
    CHEN Qiuqiang1,XIE Hongqin1,ZHOU Wen1,CHEN Jifan2,HUANG Hao1,
    2012, 31(05):  1043-1046. 
    Abstract ( 1610 )  
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    Mineralization of phenol was investigated under visible light irradiation by using the catalyst cerium doped nano-TiO2(named as Ce-TiO2). Degradation of phenol in different reaction systems was discussed,and the influences of reaction conditions,such as phenol concentration,solution pH,catalyst dosage and reaction temperature were also evaluated. The catalytic results showed that 35.8% TOC removal of phenol were achieved under visible irradiation at a reaction condition of cerium doped amount of 1.00%,calcination temperature at 700 ℃,calcination time for 3 h,pH 5 and 1.0 g/L catalyst dosage.
    Study on the hydrodesulfurization and the hydrodenitrogenation over Al2O3-ZrO2 supported Ni2P catalysts
    LI Feng1,SONG Hua1,ZHANG Huayang2
    2012, 31(05):  1047-1051. 
    Abstract ( 1374 )  
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    A series of Al2O3-ZrO2 composite oxides were prepared by impregnation-deposition method. Ni2P/Al2O3-ZrO2 catalysts were prepared by temperature-programmed reduction in a H2 flow. The supports and catalysts were characterized by X-ray diffraction(XRD),N2 adsorption-desorption and X-ray photoelectron spectroscopy(XPS). The effect of composite oxides on the performance of Ni2P catalysts was studied by thiophene hydrodesulfurization and pyridine hydrodenitrogenation. The results showed that the introduction of small amounts of ZrO2 on the surface of Al2O3 would not only keep high surface area of γ-Al2O3 but also reduce the contact between P or Ni and the surface of Al2O3,and therefore,promote the formation of Ni2P. Ni2P/Al2O3-ZrO2 catalyst made from Al2O3-ZrO2 support with 20% ZrO2 exhibited the highest activity. And the activity of catalyst would decrease with higher calcination temperature of supports.
    Nanosized SiO2/TiO2 particles prepared by microemulsion method and its photocatalytic activity
    CHEN Shixiang,LIU Hong,WANG Cui,PENG Xiuda,WANG Xiaohua
    2012, 31(05):  1052-1056. 
    Abstract ( 1560 )  
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    A SiO2/TiO2 composite photocatalyst was prepared by microemulsion method using inorganic polymerized silicate as the silicon source and titanium sulfate as the titanium source. The influence of preparation conditions on photocatalytic activity was investigated,and the photocatalyst was characterized by SEM,FTIR,XRD and BET. The results prove that a strong interaction exists between SiO2 and TiO2 particles,the formation of Ti—O—Si bond inhibits the TiO2 particle growth and also defers the transformation of TiO2 from anatast to rutile phase. The photocatalytic degradation of dyes,such as methyl orange,shows that the photocatalytic activity of SiO2/TiO2 is not improved along with higher propotion of TiO2. when the amount of substance ratio between Silicon and Titanium was 1∶1,and the photocatalyst was hydrothermal synthesized for 2.5 h at 160 ℃,the decoloration rate of methyl orange under UV light irradiation for 15 minutes over the SiO2/TiO2 photocatalyst could reach 85.5%,which has better photocatalytic activity and higher specific surface area than the TiO2 photocatalyst prepared under the same condition.
    Preparation and photocatalytic activity of nano-nitrogen-doped TiO2
    SONG Weiwei,XUE Yongqiang,SU Lining,JU Hongbin
    2012, 31(05):  1057-1060. 
    Abstract ( 1602 )  
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    Nano-N-doped TiO2 photocatalyst was prepared by Sol-Gel method at room temperature,using tetrabutyl titanate as raw material and urea as N source. The N/TiO2 photocatalyst was characterized by X-ray diffraction(XRD),TEM,UV-Vis DRS. The results show that the N doped extended the spectral response range of nano-TiO2 particles to the visible light region. The better process parameters are that:n(n-butyl titanate) ∶n(urea) of 1∶3 and calcinate time of 3.5 h at 400 ℃,under which nano-N/TiO2 is anatase phase and its average particle diameter is 13 nm. When the photodegradation of methyl orange,the optimal pH is 4.0,degradation rate of methyl orange can reach 70.5% after 3 h。
    Efficient synthesis of dimethyl carbonate via the transesterification of ethylene carbonate with methanol over MgO/NaY catalyst
    NI Bei,XU Jie,XUE Bing,LIU Ping,LI Yongxin
    2012, 31(05):  1061-1064. 
    Abstract ( 1711 )  
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    MgO/NaY catalysts prepared via wet impregnation method have been investigated for the catalytic synthesis of dimethyl carbonate(DMC)by the methanol with ethylene carbonate(EC). Several techniques,including CO2-TPD,TEM,were applied to characterize the structure and basic properties of the as-synthesized catalysts. The effects of MgO loading amount,reaction temperature,reaction time,and the ratio of methanol to EC on the catalytic performance have been studied. The results demonstrated that the MgO-loading amount played an important role on the dispersion of MgO species and the basic property of catalysts. The best catalytic performance was obtained over the 12% MgO/NaY catalyst under 70 °C with a ratio of methanol to EC of 8∶1,affording a remarkable DMC yield of 89%.
    Progress of photo-responsive drug release systems(Pr-DDS)
    YU Lili,YAO Lin,YANG Liyan
    2012, 31(05):  1065-1070. 
    Abstract ( 1345 )  
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    Photo-responsive drug delivery systems(Pr-DDS)stands out as a clean and noninvasive DDS. For Pr-DDS,the release of entrapped drugs can be accelerated at a specific location and time upon light-activation,which promotes maximum efficacy. The typical chromophores,incorporated into the photo-responsive drug release systems to render it susceptible to light trigger,include azobenzene(photoisomerization type),spiropyran(formation of zwitterionic species),coumarin(formation of the photo-cross-linking structure),and nitrobenzyl esters(conversion from hydrophobic to hydrophilic block). In this paper,the progress in Pr-DDS development has been reviewed according to their different chromophores,and their application is also involved. Among these four Pr-DDS,Azo,as the representatives of the photoisomerization type,is the most widely studied one,which involves themicelles,vesicles,hydrogels,liposomes,etc. And nitrobenzyl ester,as the representatives of the conversion from hydrophobic to hydrophilic block type,has attracted wide attention for the two-photon response capability. In conclusion,although great progresses had been made on Pr-DDS,but there were still many problems,including how to improve the biocompatibility,and how to achieve feasible targeted light-controlled release in vivo.
    Preparation of quantum dot-molecular beacon and its application in nucleic acid detection
    JIA Huning,YE Baofen,YAN Zhengyu
    2012, 31(05):  1071-1075. 
    Abstract ( 1608 )  
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    Quantum dots(QDs) have substantial advantages over organic dyes,including high stability against photobleaching,tunable colors by changing particle size,a single wavelength for simultaneous excitation of different-sized QDs and narrow emission peaks. Replacing the organic fluorophores of the conventional molecular beacon with QDs will overcome its many shortcomings. Quantum dot-molecular beacon is not only sensitive in measurement and stable against photo degradation,but also can be applied for multi-detection. In this paper,the development of quantum dot-molecular beacon in recent years is introduced. The types of MBs,linkage strategies,fluorescence quenchers and the characterization of quantum dot-molecular beacon were summarized. Moreover,its applications on nucleic-acid diagnostics are discussed,including multiple SNP detection,real-time monitoring on the living cells.
    Study on the properties of environmental friendly flame retardant high resilience polyurethane foam
    WANG Guangheng,YANG Shuilan,NIU Hongmei,LIU Guoyang
    2012, 31(05):  1076-1081. 
    Abstract ( 1715 )  
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    The development of environmental friendly polyurethane foams is a focus in polyurethane industry. By introducing soy protein isolate(SPI)and flame retardant polyols into polyurethane(PU),environmental friendly flame retardant high resilience flexible polyurethane foams were prepared by free foaming. The effects of SPI content and addition manner on the physical,mechanical,biodegradability,and flame retardant properties of PU foams were investigated. The results show that,introducing SPI by adding not by substituting for polyols is an effective way to improve the performance of PU foam. By adding a small amount of SPI,the open cell ratio,elongation at break,resilience,comfort factor,density,and indentation force deflection value of PU foam are increased,while the tensile strength,limited oxygen index,and compression set value are slightly affected. SPI changes the structure of rigid segments,hence effectively enhances the biodegradability of PU foam.
    Hydrogen-bonding and compatibility of chitosan/polyvinyl alcohol blend films
    ZHU Erbin,XIN Meihua,LI Mingchun,LIN Jiafu
    2012, 31(05):  1082-1087. 
    Abstract ( 1797 )  
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    Chitosan(CS)/polyvinyl alcohol(PVA)blend films with different compositions were prepared by solution casting technical using 2% acetic acid/water as a solvent. The structure,hydrogen-bonding,thermal behaviors and crystallization of CS/PVA blend films were systematically investigated by variable temperature FTIR,TGA,DTA,DSC and WXRD. It indicated that strong hydrogen-bonding interactions existed between CS and PVA,leading to the increase in thermal stability of CS,the decrease in crystallinity of PVA,and enhancement of the compatibility of CS and PVA. When the weight ratio of CS / PVA blend films was 10/0,7/3,5/5,3/7 and 0/10,the initial decomposition temperature of blends was 244 ℃,257 ℃,260 ℃,262 ℃ and 285 ℃ correspondingly. The melting temperature of PVA was decreased from 193 ℃ to 173 ℃. The glass transition temperature was increased from 74.2 ℃ to 80 ℃,and the crystallinity Xc declined from 3.57% to 1.97%.
    Preparation and performance research of anti-fouling composite polyamide nanofiltration membrane
    SUN Zhimeng1,2,REN Xiaojing2,ZHAO Kehui2,ZHANG Zhongguo2,
    2012, 31(05):  1088-1095. 
    Abstract ( 1635 )  
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    A composite polypiperazine-amide nanofiltration membrane,supported by polysulfone(PSF)ultrafiltration membrane,was prepared via interfacial polymerization of piperazine(PIP)and trimesoyl chloride(TMC)in the present of polyvinyl alcohol(PVA). The effects of PVA,PIP and TMC concentration,temperature and time of heat treatment on the composite membrane were studied,and the surface structure and morphology were analyzed by scanning electron microscope(SEM)and atomic force microscopy(AFM). The experiment results showed that increasing PVA content would lead to the increase in the flux of the nanofiltration membrane,make the nanofiltration membrane more hydrophilic,and cause the surface of the nanofiltration membrane smoother. The optimal preparing condition of the composite membrane was 3.0 g/L TMC,1.0 g/L PIP,0.54 g/L PVA,1 min reaction time,and 10 min heat treatment at 50 ℃.The separation performance of self-made nanofiltration membrane,treating the solutions of Na2SO4,MgSO4,NaCl or MgCl2,was similar to that of the commercial nanofiltration membranes,such as Dow NF-270 and Synder. Furthermore,the nanofiltration membrane also showed very good separation and anti-fouling performance in the advanced treatment of deinking wastewater.
    Utilization of feruloyl esterase and xylanase for the degradation of brewers’ spent grain
    LI Xialan1,CHENG Shanying1,YANG Daoxiu1,FANG Baishan1,2
    2012, 31(05):  1096-1102. 
    Abstract ( 1501 )  
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    The optimal fermentation time of Penicillium citrinum feruloyl esterase(PcFAE)was 60 h and its activity was 40.8 mU/mL when the Brewers’ Spent Grain(BSG)was used as the sole carbon source for Penicillium citrinum. One gram of alcohol-insoluble residue(AIR)of Brewers’spent grain(BSG)was processed by the solution of crude xylanase(XG180)(47.5 U/mL,15 mL)for 12 hours at the condition of the material-liquid ratio 1∶30(W/V),pH 5.0 and 45 ℃,respectively. And then the solution of crude PcFAE(40.8 mU/mL)was added and the sample was processed for another 12 h. The maximum release rate of Ferulic acid(FA)was 54.1% and the release amount of xylooligosaccharide(XOS)was 161 mg/g(BSG-AIR),respectively. The results of our experiments showed that the release rate of FA and XOS from BSG-AIR increased significantly as the PcFAE could coordinate with the xylanase and enzymolysis process was also conducive to the degradation of BSG.
    Application of triphenylphosphine in the preparation of furfural from corncob
    YUE Liqing1,2,XIAO Qinggui2,WANG Tiangui1,XU Hongbin2,CAO Hongbin2,ZHANG Yi2
    2012, 31(05):  1103-1108. 
    Abstract ( 1055 )  
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    The application of triphenylphosphine as an additive in the production of furfural was researched. The effect of the amount of triphenylphosphine on furfural yield was investigated in the range of 0.05%—0.5% of corncob’s weight. The result shows that furfural yield reached 86% with triphenylphosphine’s amount of 0.25% in corncobs. Furfural yield was improved 20—25 percent compared to the traditional process. Therefore,the addition of triphenylphosphine could improve furfural yield obviously,which would have a good prospect in furfural production.
    Study on a new furfural preparation process based on steam-explosion way
    LI Zhisong,ZHU Bin
    2012, 31(05):  1109-1112. 
    Abstract ( 1270 )  
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    It was studied that a steam-explosion way instead of an acid hydrolysis step was used in furfural production process. And the optimal parameters were obtained for the new process. Corn stalk 20 g was treated by steam-explosion under 1.4 MPa pressure and pressure-maintaining time for 4 min. The obtained material was extracted by 60 mL hot water(80 ℃)lasting 2 h. Xylose concentration was 9.96 g/L in the extraction water. The extraction ratio of xylose was 2.79%. The extraction water 350 mL,toluene 30 mL and 5% dilute sulfuric acid 10 mL were mixed and treated by reaction distillation under 165℃ for 3h.The furfural yield was 84%. The total mass yield of furfural was 2.2%. The three waste amounts produced from the said process were decreased largely.
    Advances in the synthesis of 3-picoline via acrolein/ammonia reaction
    ZHANG Xian1,CHAO Zisheng1,HUANG Denggao1,LUO Caiwu1,LIU Wei1,WANG Kaiming2,PAN Jingang3
    2012, 31(05):  1113-1120. 
    Abstract ( 1475 )  
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    This paper reviewed the synthesis of 3-picoline via the reaction between acrolein and ammonia. It was reported up to now that there are mainly three approaches for the synthesis of 3-picoline from the reaction of acrolein with ammonia,i.e.,the liquid-phase reaction in stirring tank reactor,the gas-phase reaction in fixed-bed reactor and the gas-phase reaction in fluidized-bed reactor. The paper described the general features of these reaction processes,with comments on their advantages and disadvantages and the related catalysts. It addressed particularly the key issues in the reaction process of acrolein/ammonia to 3-picoline. The foreground of the mesoporous material and solid acid catalysts applied to the reaction and the mechanism researches of 3-picoline prepared from acrolein were also prospected,the mesoporous material and solid acid catalysts applied to the reaction and the mechanism researches were thought to one of the development direction.
    Synthesis of acetylsalicylic acid catalyzed by carbon-based solid acid
    ZHAN Changchao1,2,CAO Xiaohua1,2,YAN Ping1,WANG Jianbo2,YU Zujin1,JIANG Xiaoping1
    2012, 31(05):  1121-1125. 
    Abstract ( 1593 )  
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    Carbon-based solid acid catalysts synthesized from starch and p-toluene sulphonic acid were characterized by FTIR,TG,BET,SEM and EDS. Its catalytic activity and effect of conventional heat and microwave heat on yield of acetylsalicylic acid were studied. The better condition was determined with single factor tests,which is as follows:the molar ratio of acetic anhydride to salicylic acid was 1.5∶1,the weight ratio of carbon-based solid acid to salicylic acid was 5.8%,acylation reaction temperature was 76—80 ℃,reaction time was 25 min under conventional heat. The yield of acetylsalicylic acid was 82.1% and kept 78.2% after used five times under conventional heat. The carbon-based solid acid catalyst has high catalytic activity and retrievability under conventional heat,which are better than that of microwave heat.
    Dehydration of 1,4-butanediol to tetrahydrofuran catalyzed by H9P2W15V3/C
    CAO Xiaohua,YAN Ping,XIE Baohua,XU Changlong,QIU Lixia
    2012, 31(05):  1126-1129. 
    Abstract ( 1088 )  
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    Tungstovanadophosphoric heteropoly acid with tri-vanadium-substituted Dawson structure supported by activated carbon was prepared by impregnation method and characterized by IR. Its catalytic performance was studied in the catalytic synthesis of tetrahydrofuran from 1,4-butanediol. The optimal reaction condition was obtained by orthogonal experiments as mass ratio of 1,4-butanediol to catalyst 100∶3.93,reaction temperature 185—190 ℃ and reaction time 40 min,under which,the yield of tetrahydrofuran reached 93.30%. The catalyst could be reused for 3 times and the yield was still above 90.94%. This approach provides a green,safe,operation simple and highly active dehydration process to produce THF.
    Synthesis and characterization of (S)-3-benzoylthio-2-methylpropionic acid
    RUAN Jiuyong1,QU Minjie1,JIANG Dianpin2,LI Chengbin2,XU Dongchao1,GUO Jing1
    2012, 31(05):  1130-1133. 
    Abstract ( 1052 )  
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    3-benzoylthio-2-methylpropionic acid racemate was synthesized by condensation and hydrolysis-esterification reaction of thioacetic acid with methacrylic acid,then (S)-3-benzoylthio- 2-methylpropionic acid was obtained by chemical resolution. The influencing factors in each step were taken into account. The results showed that 3-acetyl-mercapto-2-methyl-propionic acid(condensate A)was obtained with the yield of 95.6% when the molar ratio of thioacetic acid to methacrylic acid was 1.4∶1,reaction time was 2h and reaction temperature was 93 ℃. Condensate A was added into 11.8% sodium hydroxide aqueous solution to make it hydrolysis with kettle temperature below 20 ℃,then sodium salt was put into the kettle,and the same mole benzoyl chloride was dropped as condensate A into the kettle under low temperature. Two hours later,the product was obtained by acidifying the reaction mixture with hydrochloric acid,the yield of product in hydrolysis-esterification reaction was 96.7%. D-(+)-N-benzyl-α-phenylethylamine was used as the resolving agent to split the product,the yield in this step was 36%. Taking all the procedures above into consideration,the yield of final product was 33.3%. The product was characterized with MS,1H NMR and FT-IR analysis,and proved to be with high crystallinity by X ray diffraction.
    Source analysis of dio-sodium salt in fatty acid methyl ester sulfonate and amelioration
    JIANG Huiliang,WANG Xiangming
    2012, 31(05):  1134-1136. 
    Abstract ( 958 )  
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    The content of di-sodium salt(DSS)in every step of MES’s synthesis was measured,the maximal decrease of DSS is in reesterification stage,the maximal increase of DSS is in neutralization stage. It could be resulted from the methanol introduction in reesterification stage, strong alkaline environment and higher temperature in neutralization stage. Meanwhile,improvement is also proposed for every stage in ameliorated method. By optimizing the experiment,the optimal condition for every stage was obtained as,bleaching temperature 75 ℃,reesterification time 6h,the mole ratio of methanol to fatty acid methyl ester sulfonic acid 30∶1,neutralization pattern,dry neutralization by sodium carbonate powder when the content of di-sodium salt is the lowest.
    Experimental study on the synthesis of 3-methyl salicylic acid from carboxylated o-cresol in supercritical or subcritical carbon dioxide
    ZHANG Ping1,XU Mingxian2,YU Jingyi1,LIN Chunmian1
    2012, 31(05):  1137-1142. 
    Abstract ( 1206 )  
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    The synthesis of 3-methyl salicylic acid in supercritical or subcritical carbon dioxide has important meaning for the green synthesis of 3-methyl salicylic acid and resourcization of carbon dioxide. After comparing the catalytic activity of anhydrous potash,anhydrous sodium carbonate and so on,anhydrous potash was chosen as the best catalyst to synthesize 3-methyl salicylic acid directly from o-cresol by one-pot method in supercritical or subcritical carbon dioxide. At the condition of reaction time from 1—6 hours,catalyst′s relative dosage(nK2CO3/ nO-Cresol)from 0.05—1.25,reaction temperature from 130—270 ℃ and reaction pressure from 4—10MPa,o-cresol’s carboxylic reaction was studied in supercritical or subcritical carbon dioxide. The result showed that the conversion of o-cresol and the yield of 3-methyl salicylic acid both increased at first with the increase of time,and then the conversion became stable,but the yield decreased slightly in the end. The conversion and the yield increased rapidly at first and then increased slowly with the increase of catalyst′s relatively dosage. The conversion and the yield increased rapidly at first but then decreased with the increase of reaction pressure or reaction temperature. The conversion is about 19.7% and the yield is about 17.5% under the optimal condition that reaction time was 3 hours,catalyst′s relatively dosage was 0.5,reaction temperature was 190 ℃ and reaction pressure was 8 MPa. In addition,a possible reaction mechanism was proposed.
    Research on the absorption of CO2 from flue gas and the desorption of decarbonization solution using ammonia method
    MA Shuangchen,WANG Mengxuan,MENG Yanan,CHEN Weizhong,LU Dongli,HAN Tingting
    2012, 31(05):  1143-1148. 
    Abstract ( 1510 )  
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    CO2 capture using ammonia method has become an emerging research hot point due to its characteristics of high removal efficiency,low cost,high absorption capacity etc. The mechanisms about CO2 capture by ammonia method and solution desorption after decarbonization were introduced in the paper. Research progress in this process was reviewed. Several problems affected the application of this technology were analyzed,such as mechanism research,ammonia leakage and energy consumption etc. Industrial test and combined desulfurization and decarbonization should be carried out in near future,so as to push forward the industrial application as soon as possible.
    Advances of technologies for offshore oilfield wastewater treatment
    DU Chun’an,PAN Yongqiang,WU Xiaoling
    2012, 31(05):  1149-1153. 
    Abstract ( 1594 )  
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    In this paper,the advances and applications of treatment technologies for offshore oilfield wastewater were summarized. The seawater treatment technologies for injection,such asincluding sulphate removal from injection water,and subsea raw seawater injection are introduced. Re-injection and discharged wastewater treatment technologies are also discussed,among which flotation cyclone separation,filtration,extraction and oxidation technologies are especially addressed. The development trend of improvement and optimum combination of existing technologies were put forward.
    Mechanism and kinetics analysis of the phenol degradation by Fe(Ⅱ)-EDTA/K2S2O8 process
    ZHOU Zuoming1,2,ZHOU Qi1
    2012, 31(05):  1154-1159. 
    Abstract ( 1658 )  
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    The affecting factors on phenol removal by Fe(Ⅱ)-EDTA/K2S2O8 process were studied,and the oxidation mechanism and reaction kinetics were analyzed. The results showed that the forms of iron ion and oxidant,the addition of chelant and ultraviolet have obviously effect on the oxidation of phenol. When EDTA dosage was 0.5 mmol/L,Fe(Ⅱ)dosage was 1.0 mmol/L,K2S2O4 dosage was 2.0 mmol/L,and initial pH values was 7.0,the phenol(C0=100 mg/L)degradation rate reached 71.48% at 60 ℃ for 60 min by Fe(Ⅱ)-EDTA/K2S2O8 process,under the same condition,ultraviolet radiation could increase the degradation rate to 89.38%. Mechanism and kinetics analysis showed that phenol was mainly degraded through the complex reaction with Fe4+ in Fe(Ⅱ)-EDTA/K2S2O8 process.
    Coating wastewater treatment by aerobic granular sludge in SBR
    LIU Shaogen,SUN Jing,CHENG Xiongjian,REN Yibo
    2012, 31(05):  1160-1164. 
    Abstract ( 1176 )  
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    In order to study the feasibility of coating wastewater treatment by aerobic granular sludge in SBR,aerobic granular sludge cultivated in domestic wastewater was used as inoculum and gradually acclimated by the coating wastewater. In this way,the shape,physicochemical properties and pollutant removal ability of acclimated granular sludge were observed. The results showed that five weeks later, the acclimated granular didn’t disintegrate but in a more compact structure,white color with an average diameter 1.5 mm,MLSS 8000 mg/L and SVI30 28 mg/L,which represented that both the settling performance and the biomass had been improved. When the reactor operated about 45 days, the pollutant removal ability was found to be in apparent and stable state with effluent concentration of COD,NH4+-N, PO43- -P below 100 mg/L,10 mg/L,1.0 mg/L,which achieved the secondary standard of “Integrated Wastewater Discharge Standard” (GB 8978—1996) as well as the good pollutant removal effect synchronization.
    Separation technology for methanol-dimethyl carbonate system by double column distillation
    YANG Deming,WANG Yang,LIAO Qiao,ZHANG Xuejie
    2012, 31(05):  1165-1168. 
    Abstract ( 1819 )  
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    Two kinds of double-column distillation process,double effect heat integration distillation and separate heat pump distillation,for separation of methanol-dimethyl carbonate system were simulated based on the methanol-dimethyl carbonate system azeotropic character. The binary interaction parameters of Wilson equation were fitted against the reported experimental data of methanol-dimethyl carbonate system. Based on the minimum annual total cost,simulations for the two kinds of double-column distillation process were performed by Aspen Plus software to achieve the optimal condition. The simulation results showed that the two kinds of double-column distillation need lower energy consumption and less annual total fee. Compared with double effect heat integration distillation,separate heat pump distillation can save total capital fee by 2.69% and annual total fee by 17.33% .
    Industrial study on hydrogenation process of cracking C9
    WANG Tinghai1,XIANG Yongsheng1,LIU Ruigang2,LI Pingzhi1,CHANG Xiaoxin1,MA Haowen1
    2012, 31(05):  1169-1172. 
    Abstract ( 1328 )  
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    In this paper,cracking C9 gasoline from Dushanzi Petrochemical Company is used as raw material and industrial equipment condition was simulated. The results of stability and 1000h activity of LY-C9-A1+LY-C9-A2 and contrast catalyst show that diene value of LY-C9-A1+LY-C9-A2 hydrogenation products is much lower than that of contrast catalyst even under the condition that inlet temperature of LY-C9-A1+LY-C9-A2 is 5~10 ℃ lower than that of contrast catalyst. The results indicated that LY-C9-A1+LY-C9-A2 possessed better hydrogenation activity comparing with contrast catalyst. Meanwhile,the heating rate of LY-C9-A1+LY-C9-A2 is slower than that of contrast catalyst,which shows that carbon deposition rate of LY-C9-A1+LY-C9-A2 is slower and hydrogenation stability is better. In conclusion,comprehensive properties of LY-C9-A1+LY-C9-A2 are superior to contrast catalyst and enjoy predictable industrial application prospect.
    Influence factors analysis of ?-methyl styrene hydrogenation reaction in a trickle-bed reactor
    DING Hengyang
    2012, 31(05):  1173-1177. 
    Abstract ( 1334 )  
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    With α-MS,hydrogen as raw material,cumene was synthesized by catalytic hydrogenation in a trickle-bed. The work mainly investigated the influence of reaction temperature,pressure,circulation,feeding α-MS concentration,hydrogen oil ratio on hydrogenation reaction. The results showed that the reaction temperature can accelerate the reaction rate within the range of 60—120 ℃;hydrogenation reaction rate is the fastest with the pressure from 0.7 to 0.8MPa,processing capability is the largest;the improvement on hydrogen to oil ratio ensure raw materials and catalyst contact time under the premise of the reaction;the circulation rate and the concentration of the feed α-MS reaction rate can be changed but the actual processing capacity cannot be changed;the stability of catalytic activity is the premise of the hydrogenation. The constrains for bed design processing capacity is the key for the reduction of current hydrogenation effect and the limitation of production capacity.