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Table of Content
05 December 2016, Volume 35 Issue 12
    Synthesis and application of S-doped carbon materials
    CAO Weiran, LI Yulong, ZHOU Ying, LIU Ruifeng, MA Dongju, QIU Jieshan
    2016, 35(12):  3727-3734.  doi:10.16085/j.issn.1000-6613.2016.12.001
    Abstract ( 551 )   PDF (845KB) ( 1008 )  
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    Heteroatom doping of carbon materials can modify their surface properties and thus improve their performance. By changing the precursors and optimizing the process,we could prepare plenty of S-doped carbons materials with different structures and excellent performance. This review presents the latest advances on the synthesis of S-doped carbon materials from various precursors. Special emphasis is put on the influence of precursors and synthesis process on the form of intrinsically doped sulfur atoms and the structure of carbon materials. The effect of sulfur doping on the performance of carbon materials for supercapacitors and electrocatalyst are also discussed. The controllable synthesis of S-doped carbons still remains a challenge although various new synthetic strategies have been applied to the brand-new field. Preparing S-doped carbon from cost-effective and carbon-rich heavy organic matters and controlling the synthetic process might be important for its large-scale application.
    Recent developments in microwave-assisted chemical separation processes
    LI Hong, CUI Junjie, LI Xingang, GAO Xin
    2016, 35(12):  3735-3745.  doi:10.16085/j.issn.1000-6613.2016.12.002
    Abstract ( 436 )   PDF (1341KB) ( 827 )  
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    It has been a hot topic in the study of chemical separation process to strengthen the chemical separation technology and to realize the energy conservation and emission reduction in the separation process. The study of separation processes enhanced by microwave field is very active in recent years. In this paper,the mechanism of microwave on matters were explained,and the advantages and characteristics of microwave heating compared with conventional heating were discussed. The strengthening effects and application progress of microwave field in extraction,drying,desorption/adsorption,distillation and reactive distillation separation process were introduced systematically,and the strengthening mechanisms of microwave field in these separation processes were summarized and analyzed. The analysis showed that the application of microwave in chemical separation process had the characteristics of high heating speed,high product quality,low energy consumption and easy-control production process. Moreover,the lack of research of microwave in the field of distillation/evaporation and reactive distillation was pointed out. In addition,this paper suggested that a lot of experiments and the corresponding theoretical support were needed to verify whether the microwave was beneficial to the distillation process or reactive distillation process.Meanwhile,the development of microwave in the field of separation was analyzed and forecasted.
    Application of filtration technology in slurry oil clarification
    ZHANG Xiaofang, BU Yifeng, MEN Zhuowu
    2016, 35(12):  3746-3754.  doi:10.16085/j.issn.1000-6613.2016.12.003
    Abstract ( 465 )   PDF (688KB) ( 1507 )  
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    In catalytic reactions like catalytic cracking,hydrocracking,the catalyst fines will cause equipment abrasion and fouling in the downstream,and also can reduce the value of oil product. For Fischer-Tropsch synthesis,separating the synthesis wax from gas-liquid-solid mixture in slurry bubble column reactor is difficult and utmost important for the process. Above all,removing the catalyst particulate in slurry oil is crucial to the stability of the units and the product quality. This paper reviews the development and application status of slurry oil filtration technologies,concludes the filtration characteristics like machining performance and filtering accuracy for two types of filter cartridge,which takes MOTT and Pall as representatives. The technologies in terms of operation condition,efficiency and backwash method,etc. are compared to have an analysis on filtration process and to figure out the influences of process and parameters on filtering effect and technology choice. This may provide references when make a choice on filter cartridge and process in slurry oil filtration of petrochemistry and Fischer-Tropsch synthesis.
    Progress on the application of artificial neural network in chemical industry
    SONG Hongyang, SUN Xiaoyan, XIANG Shuguang
    2016, 35(12):  3755-3762.  doi:10.16085/j.issn.1000-6613.2016.12.004
    Abstract ( 586 )   PDF (589KB) ( 1253 )  
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    Artificial neural networks were the important part of artificial intelligence,which had a broad space in improving the chemical process of traditional production techniques diagnosis of lag,difficult to optimize and control,large property estimation error and could not deal with complex nonlinear problems. Artificial neural networks have drawn much attention because of superior robustness,fault tolerance,approximation of complex nonlinear correlations,parallel processing and adaptive learning. Artificial neural networks have been applied to chemical processes in the following areas:fault diagnosis,process control and optimization,quality control,quantitative structure-activity/property correlation analysis,property estimation,expert system and clustering analysis. This paper summarized the theory and development history of artificial neural network,and conducted meta-analysis of the literature on the principles and the development of artificial neural networks in chemical processes. Finally,the paper pointed out that the deep learning algorithm had advantages of high-performance and high speed,and then discussed that the future study of neural networks in chemical process would be the direction and hot topic in the development and application of deep learning algorithm.
    A study on flow boiling resistance of nanorefrigerant in rectangular microchannels
    LUO Xiaoping, ZHANG Lin, LIU Bo
    2016, 35(12):  3763-3770.  doi:10.16085/j.issn.1000-6613.2016.12.005
    Abstract ( 376 )   PDF (990KB) ( 452 )  
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    The flow boiling characteristics were experimentally investigated through the aluminum-based rectangular microchannels with a hydraulic diameter of 1333μm,using Al2O3-R141b nanorefrigerants with a different partical of 0.2%,0.5% and 0.8%(mass fraction) and pure refrigerant as the working fluids. The effect of concentration on the two-phase frictional pressure drop were investigated by comparing the surface energy of heat transfer surface before and after experiment. Results showed that when nanorefrigerants with a different particles of 0.2%,0.5% and 0.8% were working fluids,the two-phase frictional pressure drop was lower than pure refrigerant under the same experimental conditions,and the biggist drop were 11.6%,14.8% and 19.2%. Nanoparticles adhered to the surface after experiment and increased the surface energy of heat transfer surface by 1.26 times,1.44 times and 1.91 times,respectively. It reduced the roughness and improved the surface wettability of heat transfer surface,made two-phase frictional pressure drop decrease. Based on the comparison of experimental data with predicted value of models,modified Qu-Mudawar,the new correlation had a better predict ability. The mean absolute error decreased to 9.78%.
    Research on the distribution characteristics of the salting-out particles in the steam turbine nozzle
    LI Yong, HU Pengfei, CAO Lihua
    2016, 35(12):  3771-3776.  doi:10.16085/j.issn.1000-6613.2016.12.006
    Abstract ( 339 )   PDF (1471KB) ( 636 )  
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    To have a better understanding of microscopic behavior of salting-out particles in a steam turbine,a high-pressure grade nozzle was employed in a supercritical steam turbine as a research object and simulated the distribution of salting-out particles in the flow field from a steam turbine nozzle using CFD-PBM method. The average diameter,component number and the concentration distribution of salting-out particles were obtained,respectively. The simulation results show that the salting-out particle diameter varied little near the nozzle entrance,while the particle diameter gradually increased along the flow direction,and the growth rate of the particle diameter slowed down gradually near the nozzle outlet. In addition,due to the salting-out particles interaction,the component number distribution of particles with 20μm diameter decreased gradually along the flow direction,while the component number distributions of particles with 80μm and 140μm diameters were opposite. A high component distribution with 20μm diameter particle existed in the suction side,and with 140μm diameter particle existed in the pressure side. From the suction side to the pressure side,the concentration of the salting-out particles gradually increased,and it eventually formed a high concentration area near the pressure side.
    Formation kinetics of cyclopentane-methane hydrate in NaCl solution with a bubbling equipment
    LÜ Qiunan, SONG Yongchen, LI Xiaosen
    2016, 35(12):  3777-3782.  doi:10.16085/j.issn.1000-6613.2016.12.007
    Abstract ( 352 )   PDF (1736KB) ( 505 )  
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    The formation kinetics of cyclo-pentane(CP)-methane hydrate in NaCl solution were studied using a bubbling equipment. The effect of gas-flow rate,temperature and pressure on the hydrate formation rate and the effect of gas-flow rate on the gas conversion rate were investigated. The results showed that increasing the gas-flow rate,pressure and decreasing the temperature could enhance the hydrate formation rate. But the gas-flow rate affected the gas conversion rate. If the gas-flow rate was too high,the gas entering the reactor was discharged before completing the reaction,which yielded the low gas conversion rate. The observation of the process of CP-CH4 hydrate found thatthe hydrate crystals first generated in the CP/water interface,then grew gradually in internal gas phase until the hydrate shell broke and the bubbles escaped.
    Thermal dynamics analysis on the organic Rankine cycle (ORC) with internal heat regenerator at superheated and subcooling conditions
    XU Rongji, ZHANG Xiaohui, YAN Meiyu, WANG Ruixiang, XU Shuhui
    2016, 35(12):  3783-3792.  doi:10.16085/j.issn.1000-6613.2016.12.008
    Abstract ( 410 )   PDF (951KB) ( 864 )  
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    Internal heat recovery is a simple and effective way to improve the thermal performance of basic organic Rankine cycle(ORC). Thermodynamics regularity of the cycle is changed due to the process changes of the cycle. The heat recovery process and mechanism of the internal heat regenerator was deeply analysed and R245fa was used as working fluid. A new method that can calculate the performance of the internal regenerator was proposed based on logarithmic temperature difference. The effects of superheat and subcooling temperature on the thermal performance of the IHORC were thermodynamicly analyzed. The results indicated that the evaporation and condensation load was reduced and the thermal efficiency of the cycle was improved. The cycle efficiency and the expander work output were increased almost linearly with the increase of the superheating temperature. According to the subcooling temperatures,there were two kinds of sulbcooling:subcooling and deep subcooling. Under supercooling condition,cycle efficiency gradually decreased,evaporation and condensation load gradually increased with the increase of the subcooling temperature though the heat transfer and efficiency of the regenerator gradually increased. Under deep supercooling condition,for the reason of the heat recovery the cycle efficiency and the heat transfer and efficiency of the regenerator increased with the decrease of the evaperation and condensation load. The critical point of subcooling and deep subcooling depended on the outlet steam dryness. It was deep subcooling when the dryness of less than 1. The recovered heat was restricted by the exhaust gas. The internal regenerative ORC was suitable for conditions of high temperature difference between evaporation and condensation temperature,overheating and deep subcooling.
    Pool boiling heat transfer on superhydrophilic and superhydrophobic surfaces
    ZHENG Xiaohuan, JI Xianbing, WANG Ye, XU Jinliang
    2016, 35(12):  3793-3798.  doi:10.16085/j.issn.1000-6613.2016.12.009
    Abstract ( 455 )   PDF (2630KB) ( 876 )  
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    Experiments were conducted to study the effect of super hydrophilic/hydrophobic surface on the pool boiling heat transfer. The superhydrophilic surface was prepared by H2O2 oxidation and the superhydrophobic surface was prepared by ammonia immersion and high molecular material modification. In the experiments a high speed camera was used to record the process of bubble growth,using water as the working fluid at atmosphere pressure. It is found that for superhydrophobic surface the bubbles were easy to generate and not easy to detach at the onset of nucleate boiling accompanied by good heat transfer performance and low surface superheat. The surface superheat was only 2.4K. With the increase of heat flux,the bubbles were easy to merge and form large ones,which block the heat transfer and make surface have low critical heat flux(CHF). However,for superhydrophilic surface the existence of micro-nano sheet structure increased the surface roughness,it not only increased heat transfer area and the number of nucleate sites,but also made surface have superhydrophilic characteristic. So the bubble departure frequency was large and the boiling heat transfer was enhanced greatly. The maximum heat transfer coefficient was nearly 1.7 times than that of plain surface and the CHF can be improved to 131.0W/cm2,which showed better heat transfer performance in pool boiling.
    The strength analysis of epoxy glass fiber reinforced plastic tube based on the theory of Tsai-Hill
    XU Kunpeng, HUI Hu
    2016, 35(12):  3799-3806.  doi:10.16085/j.issn.1000-6613.2016.12.010
    Abstract ( 365 )   PDF (7126KB) ( 243 )  
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    Epoxy glass fiber reinforced plastic(Epoxy-GFRP) tube was designed in accordance with the engineering experience currently,but it was lacking of systematic study. In order to effectively evaluate the safety of Epoxy-GFRP tube support structure and to design and check it reasonably,the numerical simulation and experimental research was carried out in this paper. At first,low temperature mechanical properties test of Epoxy-GFRP material was carried out according to the test methods of GFRP properties. Then the vessel was simulated by using nonlinear finite element method,taking the strain-strengthening transportable vacuum insulated vessel as research object and considering the different transportation environment. Epoxy-GFRP tube was checked by using the Tsai-Hill strength theory. Experimental results showed that Epoxy-GFRP material has good compressive properties in low temperature environment,but low shear resistance. The simulation results showed that Mises equivalent stress of support structure was larger than that of other conditions when low temperature liquid tanker suffers bumper-to-bumper traffic conditions in the process of actual transportation. The Mises equivalent stress of Epoxy-GFRP tube near the fixed end support in the lower vessel was larger than that of other locations under different conditions. As the strain-strengthening transportable vacuum insulated vessel's main support structure,Epoxy-GFRP tube conforms to the requirements of transportation safety that its intensity checking value is far less than one under different conditions.
    Study on flow and heat transfer characteristics of nano-fountain based on thermal comfort
    WAN Yongliang, QI Cong, LI Chunyang, HAN Dongtai
    2016, 35(12):  3807-3817.  doi:10.16085/j.issn.1000-6613.2016.12.011
    Abstract ( 305 )   PDF (2613KB) ( 642 )  
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    There were few researches about the flow and heat transfer characteristics of fountain based on thermal comfort of micro-regional,so a new kind of fountain model named "nano-fountain" was established in a limited cylinder space to investigate the associated characteristics,which has high thermal conductivity and two phases(H2O-air and diamond-ethylene glycol[EG]/H2O nanofluid-air). Then the flow and heat transfer characteristics of H2O-air and diamond-EG/H2O nanofluid-air were studied respectively with different nanoparticle volume fractions and Re numbers. The effects of local temperature,streamlines distribution,average temperature as well as the flow and heat transfer characteristics were discussed. In addition,thermal comfort was evaluated according to the ASHRAE standard 55-1992 and standard ISO7730. The results showed that heat transfer enhancement increases with the increase of Re numbers and volume fractions in different degrees,and thermal comfort also increases. Diamond-EG/H2O nanofluid showed larger enhancement than H2O,and could enhance the heat transfer by 1.5% and 2.8% respectively at Re=1.0×105 and Re=1.2×105;In addition,it could enhance the heat transfer by 11.5% when nanoparticle volume fraction increases from v=3% to 5% at Re=1.4×105. Thus it showed larger enhancement in lower volume fraction at lower Re number,and heat transfer enhancement showed more obvious in large volume fraction at larger Re number.
    Dynamic behavior of droplets impacting on microstructured hydrophobic surfaces
    SHI Qiming, JIA Zhihai, LIN Qiyan
    2016, 35(12):  3818-3824.  doi:10.16085/j.issn.1000-6613.2016.12.012
    Abstract ( 380 )   PDF (2777KB) ( 1126 )  
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    The dynamic behavior of droplets impacting on micropillared and micropored surfaces was investigated in this paper. The results showed that when the droplet impacted on the micropillared surface,the droplet appeared the spreading and retraction processes. With the increase of Weber number(We),the spreading diameter increased. Meanwhile,the satellite droplets appeared. However,the time to reach the maximum spreading diameter was the same. When the droplet with the same velocity(the same We) impacted on micropillared surfaces with different pitch between micro pillars,the maximum spreading diameter decreased with the increase of the pitch,and the wetting state was instability. The wetting state transited from the Cassie state to the Wenzel state during the spreading process. When the pitch was small,The smaller the adhesion work is,the more likely to occur to the Cassie state. Moreover,the dynamic behaviors of a droplet impacting on micropored hydrophobic surfaces were compared with the micropillared surfaces. The droplet was spreading and retracting on micropored surfaces. In the impacting process,the wetting state did not transit into the Wenzel state. The phenomenon was analyzed by using the established physical model.
    A performance evaluation factor of heat exchanger network based on field synergy
    ZHANG Chunwei, CUI Guomin, CHEN Shang
    2016, 35(12):  3825-3829.  doi:10.16085/j.issn.1000-6613.2016.12.013
    Abstract ( 300 )   PDF (536KB) ( 226 )  
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    The global optimization of heat exchanger network(HEN)is significantly difficult resulting from the non-convexity and non-linearity of the model and constraints in the problem. A performance evaluation factor of heat exchanger network was established from the perspective of uniformity principle based on the field synergy theory to simplify the synthesis process of heat exchanger network and obtain efficient optimal HEN structure. Firstly,the performance evaluation factor of heat exchanger network namely was derived from the uniformity factor in a single heat exchanger to describe the uniformity of temperature difference field. Secondly,the efficiency of the performance evaluation factor of heat exchanger network was verified by three different cases,evaluating the performance of heat exchanger networks under the corresponding conditions of given network configuration and given area of heat exchangers,respectively. Finally,the results showed that the uniformity factor of temperature difference with weights,which has an obvious relation with the total heat load,could accurately describe the performance of heat exchanger networks. Generally,the performance of heat exchanger network configurations gets better under smaller value of uniformity factor.
    Laser induced fluorescence technique for observing non-isothermal falling film flow on packing surface
    HUANG Yiping, ZHOU Junchao, HUANG Jingjing, LU Xiaoyong, LIU Chunjiang, LI Pingli, GENG Yang, LIU Hui
    2016, 35(12):  3830-3835.  doi:10.16085/j.issn.1000-6613.2016.12.014
    Abstract ( 300 )   PDF (20062KB) ( 219 )  
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    Non-isothermal falling film flow is common in distillation process,which has great effect on the mass and heat transfer process on the surface of packing due to its particular property. In this paper,visualization device was set up and morphologic change of non-isothermal falling film flow on structured packing surface,in which liquid phase was heated by packing,was observed and analyzed through laser induced fluorescence system. Wetting area and film thickness were compared under different condition. Wetting area decreased remarkably with the increase of packing temperature,leading to dry plate phenomenon. The increase of local film thickness in wave trough of packing and formation of rivulet and irregular droplets were captured by LIF as well. Liquid aggregation and dispersion trajectories disappeared,weakening the redistribution and surface renewal ability. As a result,the shrinkage of non-isothermal falling film on structured packing surface is significant,which calls for enough attention to pay in industrial production for the weakening of heat and mass transfer capability.
    Development and features of process safety management (PSM) of petrochemical industry in Korea
    WANG Yuqiao
    2016, 35(12):  3836-3840.  doi:10.16085/j.issn.1000-6613.2016.12.015
    Abstract ( 426 )   PDF (399KB) ( 403 )  
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    Korea is an important country of manufacturing petrochemical products. Korean process safety management (PSM) level of petrochemical industry is in advanced one all over the world. In the paper the background for legislation of PSM system in Korea is introduced and the contents concerning PSM law are presented. Grading system is an unique feature of Korean PSM,so the evaluation procedure of the workplaces subject to the PSM regulations and grading standards are emphatically introduced. The authorities conduct an inspection or take other administrative measures taking into account the grading results. Finally,the effectiveness of KOSHA PSM is confirmed by comparison of safety situation before and after implication of PSM. The petrochemical industry in China has developed quickly in the recent two decades,especially construction of the chemical industry park. Thus,the risk management has been a key issue for Chinese government and petrochemical enterprises. Understanding the growing way of KOSHA PSM has a reference value to start and develop the process safety management for Chinese petrochemical enterprises.
    Construction of microbial fuel cells using algae
    FAN Gongduan, LIN Rujing, SU Zhaoyue, LIN Xiuyong, XU Renxing, CHEN Wei
    2016, 35(12):  3841-3847.  doi:10.16085/j.issn.1000-6613.2016.12.016
    Abstract ( 427 )   PDF (642KB) ( 479 )  
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    As global energy shortages and environmental problemsgetting worse,developing new sustainable green energy technology has become the focus attention in the world. As a new technology for sustainable development,microbial fuel cells(MFCs)constructed by algae can achieve energy saving and environmental protection. Based on the mechanism and the selection of algae species in the MFCs,this paper reviewed the state of art of MFCs constructed by algae in terms of the different roles which algae played. The capability of generating electricity and removal of water pollutant from a practical application of MFCs was illustrated in this paper. the effect of main environmental factors on the electricity output was analyzed and the current problems of algae built MFCs,such as the economic benefits,industrial and electricity production efficiency,were summarized. The prospect of future research was present to provide basics for further studying MFCs constructed by algae.
    Progress overview and performance comparison of innovative solar-assisted carbon capture technologies
    LIU Yinan, DENG Shuai, ZHAO Ruikai, ZHAO Li, HE Junnan
    2016, 35(12):  3848-3857.  doi:10.16085/j.issn.1000-6613.2016.12.017
    Abstract ( 401 )   PDF (811KB) ( 591 )  
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    In recent years,CO2 capture technologies are going through a rapid development stage from single process of CO2 separation to integrated synergy processes of CO2 separation,storage or utilization. Such a development trend also poses a higher challenge to the integration solution of solar-assisted CO2 capture technologies. This paper overviewed three innovative solar-assisted CO2 capture technologies(chemical looping combustion,hydrate-based CO2 capture and thermal chemical cycle)and made an in-depth analysis in terms of integration solution,operational parameters and performance,et al. Then based on the theory of ideal separation minimum work and second-law efficiency,a performance evaluation and comparison are conducted between innovative and conventional technologies. The results showed that,for gas mixtures with CO2 concentration from 5%~20%,absorption and thermal chemical cycle are relatively mature applications with higher second-law efficiency,and it is easy to achieve separation for hydrate-based CO2 capture because of the lowest minimum work. The innovative solar-assisted CO2 capture technologies can promote the production of carbon products and take an important step for the construction of global carbon cycle.
    Performance analysis for waste heat recovery system of ship diesel engine based on organic Rankine cycle
    ZHU Yilin, LI Weiyi, SUN Guanzhong, TANG Qiang, GAO Jing, CAO Chunhui
    2016, 35(12):  3858-3865.  doi:10.16085/j.issn.1000-6613.2016.12.018
    Abstract ( 385 )   PDF (528KB) ( 375 )  
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    An organic Rankine cycle(ORC)was designed to recover the exhaust energy from the ship diesel engine. Considering the cooling water circulation,the effects of evaporation temperature and expansion ratio on the system performance were analyzed. The economic objective function is defined as the ratio of heat exchanger area required to the system net power output. The comprehensive evaluation function is the weighted sum of the economic objective function and exergy efficiency. The optimum condensation temperature is determined by taking different optimization objectives. The results showed that the thermal efficiency increased first with the rise of evaporation temperature and then decreased. There is the optimal evaporation temperature under a constant expansion ratio. The system has different optimal condensation temperatures with different optimization objectives. It is better to determined the optimal condensation temperature using the comprehensive evaluation function as the optimization objective. The optimal evaporation temperature of the ORC system with R245fa as working fluid is 390K and the optimum condensation temperature is 316K. Besides,the expansion ratio of the system is 6.6 and the thermal efficiency can reach 12%. It was also found that the choice of working fluids had a great effect on the system performance.
    Performance of MDEA mixed amine solution removal H2S from natural gas
    AN Jiarong, MA Pengfei, TANG Jianfeng, JIANG Xue, LI Jing, ZHANG Guojun, ZHAO Mingyu
    2016, 35(12):  3866-3871.  doi:10.16085/j.issn.1000-6613.2016.12.019
    Abstract ( 405 )   PDF (674KB) ( 731 )  
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    To study the desulfurization performance of methyldiethanolamine(MDEA)+monoethanolamine(MEA)and MDEA+diethylenetriamine(DETA) mixed amine solution and provide formula and basic data for industrial gas desulfurization,a small reaction kettle was used to conduct the absorption testing. The impact of absorption temperature,absorption pressure,and regeneration temperature on the performance of amine solution removing H2S was investigated using single methyldiethanolamine(MDEA)amine solution. The experimental results showed that the optimal absorption temperature is 50℃,the optimal absorption pressure is 5MPa,and the optimal regeneration temperature is 125℃. Based on the optimized process parameters,the effect of different annexing agents to amine solution on the absorption and regeneration performance was investigated. The results showed that adding diethylenetriamine(DETA)and monoethanolamine(MEA)to the single MDEA amine solution helped improve the absorption efficiency but had a negative effect on the regeneration. The optimized formulation is 2.4mol/L MDEA+0.6mol/LMEA,2.4mol/L MDEA+0.6mol/L DETA mixed amine solutions.
    Kinetic of conversion of hemicellulose hexose to 5-hydroxymethylfurfural
    CHEN Jingping, SUN Wuxing, LIN Haizhou, RU Bin, ZHAO Yuan, WANG Shurong
    2016, 35(12):  3872-3878.  doi:10.16085/j.issn.1000-6613.2016.12.020
    Abstract ( 414 )   PDF (809KB) ( 474 )  
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    The conversion of mannose and galactose to 5-hydroxymethylfurfural(HMF)was investigated under aqueous conditions at a wide range of temperature(100~200℃)and time(10~240min)without catalyst. The results showed that higher temperature favored the decomposition of hexoses and increased the yield of HMF. At 200℃,the maximum yields of HMF for mannose and galactose were 26.82% and 22.86%,respectively,and their levulinic acid(LA)yields were at a low level below 3%. The lower yield of HMF from galactose because isomerization to tagatose is easier than that to fructose. A reaction model that hexose firstly decomposed to HMF and Humin,followed by the degradation of HMF to LA and Humin,was used to analyze the reaction kinetics. The model predicted the experiment results well. The obtained kinetic parameters revealed the varied mechanisms of HMF and Humin formation from different types of hexose. Finally,structural characterization of the Humins based on the Van Krevelen diagram and FTIR spectra showed that the Humins were furanic polymers formed by dehydration and condensation,and their structure were closely related to monosaccharide types.
    The interactions among the pyrolysis of biomass components based on the PY-GC/MS
    ZHU Lingli, ZHONG Zhaoping, WANG Jia, WANG Heng, GU Jiawen
    2016, 35(12):  3879-3884.  doi:10.16085/j.issn.1000-6613.2016.12.021
    Abstract ( 370 )   PDF (502KB) ( 702 )  
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    An analytical pyrolyzer coupled with gas chromatography/mass spectrometry (PY-GC/MS) had been proposed to investigate the interactions among the pyrolysis of biomass components. Pyrolysis experiments of cellulose,xylan(molding compound of hemicellulose),lignin,and two-component mixing components were carried out. Results showed that the primary pyrolysis product of cellulose at 600℃ and 10s was laevoglucose. The primary pyrolysis products of xylan were furfural and acetic acid,while that of lignin were phenols. In addition,the cellulose promoted the pyrolysis of xylan to yeild more acetic acid and furfural. The xylan and lignin strongly inhibited the production of levoglucose from cellulose pyrolysis. The presence of cellulose and xylan strongly contributed to the generation of phenols from lignin pyrolysis,whille lignin inhibited the pyrolysis of xylan to produce acetic acid and furfural. Experiments also discovered that the interactions among the mixing components were affected by temperature and residence time.
    Purification of Indonesian oil sands bitumen
    LUO Kuanyong, HAN Dongyun, LI Fuqi, SHI Weiwei, PANG Haiquan, CAO Zubin
    2016, 35(12):  3885-3890.  doi:10.16085/j.issn.1000-6613.2016.12.022
    Abstract ( 317 )   PDF (767KB) ( 561 )  
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    Oil sands bitumen obtained from solvent extraction contained a great amount of mechanical impurities(MI),which was harmful to the post processing of bitumen. The characterization of mineral components of MI by XRD and particle size distribution of MI by laser particle analyzer were presented. Compound reagent was developed for the removal of MI and the reaction mechanism was presented. The technology consisted of three steps,namely,dilution of bitumen by diluent(P1),purification of diluted bitumen by compound reagent(P2) and recovery of diluent(P3). In P1,under the optimal reaction conditions of 70℃,10min,m(diluent)/m(bitumen)=0.3g/g,the viscosity of diluted bitumen at 70℃ was 3.2Pa·s. In P2,under the optimal reaction conditions of V(HCl,6%)/m(diluted bitumen)=0.2mL/g,m(CaCl2)/m(diluted bitumen)=0.01g/g,70℃,mixing time 10min,settling time 20min,the mechanical impurities removal rate(MIRR)could reach 93.5%. In P3,the recovery rate of diluent was 98%,MIRR remained above 92% after diluent being recycled 5 times. The technology has the advantages of short settling time and thorough removal of MIRR in bitumen.
    Synthesis and catalytic performance of novel hyperbranched nickel catalyst in ethylene oligomerization
    WANG Jun, ZHANG Na, WANG Jiaming, LI Cuiqin, SHI Weiguang, LIN Zhiyu
    2016, 35(12):  3891-3897.  doi:10.16085/j.issn.1000-6613.2016.12.023
    Abstract ( 353 )   PDF (620KB) ( 247 )  
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    1.0G hyperbranched macromolecule was synthesized with R12-0.5G and butanediamine as starting materials. Then a novel hyperbranched salicylaldimine nickel catalyst was synthesized by Schiff's reaction and complex reaction with salicylaldehyde,nickel chloride hexahydrate and the 1.0G hyperbranched macromolecule as raw materials. The structure of the 1.0G hyperbranched macromolecule,salicylaldimine ligand and catalyst were characterized by FTIR,1H NMR,UV and MS. The performance of the hyperbranched nickel catalyst in ethylene ologomerization was also investigated. The effects of solvents,reaction temperature,reaction pressure and ratio of Al/Ni on catalytic performance in ethylene oligomerization were investigated. The results showed that the complex displayed high catalytic activity in selective ethylene oligomerization with toluene as solvent and MAO as the cocatalyst. The catalytic activity always increased with the increase of reaction pressure and Al/Ni ratio,but firstly increased and then decreased with the increase of reaction temperature.The highest activity of 5.03×105g/(mol Ni·h) was achieved and 89% of the product were C4 and C6 olefins. The reaction conditions were that temperature was 25℃,pressure was 0.5MPa,and the Al/Ni ratio was 1500. Under the same polymeric conditions,the catalytic activity of novel hyperbranched salicylaldimine nickel catalyst was lower than that of the "Broom molecule" nickel catalyst with a similar structure in ethylene oligomerization.
    Effect of preparation methods on de-NOx performance of Fe/Cu-SSZ-13 catalyst for NH3-SCR
    ZHAO Wenya, LI Yonghong, LIU Xiaojiao, ZHANG Ranran
    2016, 35(12):  3898-3906.  doi:10.16085/j.issn.1000-6613.2016.12.024
    Abstract ( 378 )   PDF (870KB) ( 610 )  
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    To solve the environmental problem of NOx in diesel exhaust,a series of Fe/Cu-SSZ-13 molecular sieves catalysts were prepared by liquid ion exchange(IE),incipient wet-impregnation (IWI) and solid-state ion exchange(SSIE)methods respectively. The catalytic performances for selective catalytic reduction (NH3-SCR) were examined and the catalysts were characterized using XRD,BET,FTIR,UV-Vis DRS,H2-TPR. The characterization results indicated that the catalysts could be used under a high space velocity,and had wider temperature range,prefect hydrothermal stability,and better high temperature SCR ability. The denitration activity of Fe/Cu-SSZ-13 catalysts was affected by their preparation method. From 150℃ to 400℃,the activity order of the SCR catalysts was:Fe(5.5%)-IE >Fe(5.4%)-SSIE >Fe(5.5%)-IWI. However,above 400℃,the activity order became:Fe(5.5%)-IE >Fe(5.5%)-IWI >Fe(5.4%)-SSIE. Moreover,the catalyst prepared by IE,with Fe concentration of 5.5%,showed the best hydrothermal stability,the largest specific surface area and the best catalytic activity,with NO conversion over 90% from 175℃ to 500℃,So Fe(5.5%)-IE was the best NH3-SCR catalysts.
    Study on 1-decene catalyzed to poly-alpha-olefins synthetic lubricant base oil by boron trifluoride
    WANG Sihan, CAO Yuanyuan, LIU Tong, SUN Enhao, GAO Han, WANG Jian
    2016, 35(12):  3907-3912.  doi:10.16085/j.issn.1000-6613.2016.12.025
    Abstract ( 466 )   PDF (495KB) ( 517 )  
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    Currently low viscosity PAO(poly-alpha-olefin) synthesis technology monopoly is acquired by foreign producers,and domestic researches in this area are rarely reported. Using 1-decene as raw material,we carried out polymerization experiments in a 1L autoclave and investigated the effects of process conditions of reaction pressure,reaction temperature,reaction time and initiator on the conversion rate and the distribution of the polymerization product. The pilot test was carried out with the optimized conditions in 200L low viscosity PAO pilot plant. Experimental results showed that when the reaction was taken place at pressure of 0.2MPa,temperature of 20℃,catalyst addition of 850g,initiator addition of 685mL(mass ratio of the 1-decene was 0.5%),reaction time of 2h,the conversion rate was more than 95% and the key component of trimers and tetramers content were greater than 80%,and the released reaction heat was approximately 6.3×104kJ. The kinematic viscosity of the obtained product at 100℃ was 4.3mm2/s,and the viscosity index was 132,while low-temperature dynamic viscosity at -40℃ was 2318mm2/s,the pour point was -60℃.The key performance indicators of the obtained product were comparable to those of foreign products.
    One-pot hydrothermal-impregnation synthesis of Pd-Fe/SiO2 catalyst with enhanced catalytic performance towards 2-ethylanthraquinone hydrogenation
    ZHUO Junlin, CAI Weiquan, LUO Xiaolei
    2016, 35(12):  3913-3918.  doi:10.16085/j.issn.1000-6613.2016.12.026
    Abstract ( 352 )   PDF (550KB) ( 708 )  
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    Fe-modified SiO2 were successfully synthesized via a moderate one-pot hydrothermal process using tetraethoxysilane(TEOS)as silicon source,and Pluronic triblock copolymer P123 or tetrapropyl ammonium hydroxide(TPAOH)as structure directing agent. Then supported catalysts of 0.3%Pd -3%Fe/SiO2 were prepared by incipient impregnation method. The phase structures,texture properties were characterized by XRD,N2 adsorption-desorption,CO pulse adsorption and the catalytic performance towards hydrogenation of 2-ethylanthraquinone was evaluated in a micro slurry bed reactor. The results showed that the prepared catalysts possess preferably mesoporous structure,structured channel,narrow pore size distribution and medium specific surface area. In the 2-ethylanthraquinone hydrogenation reaction,the prepared catalysts exhibited a high hydrogenation efficiency of 13.1g/L and a high selectivity of 66.1%,and all the catalysts still had an hydrogenation efficiency of 11g/L after 4h. In contrast,industrial catalyst was unable to work after 1.5h due to excessive side reactions,and its hydrogenation efficiency and selectivity were only 5.4g/L and 26.2%, respectively. The study also showed that when P123 was used as the structure directing agent,the doped Fe-could increase the selectivity of the catalyst,and when TPAOH was used as structure directing agent,the doped Fe-can significantly improve both the activity and selectivity of the catalyst.
    Effect of pore structure on the performance of Sn-Fe supported catalyst in denitration
    CHEN Kaige, XIAO Feng, JIANG Xiaoping, XU Qi
    2016, 35(12):  3919-3927.  doi:10.16085/j.issn.1000-6613.2016.12.027
    Abstract ( 328 )   PDF (3489KB) ( 322 )  
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    Four catalyst supports of different pore structures,namely attapulgite(ATP),activated carbon(AC),mesoporous silica(MCM-41)and titanium dioxide(TiO2),were used to prepare a series of Sn-Fe supported catalysts by the hydrothermal synthesis method with the Fe2O3 as active component,and SnO2 as auxiliary active component. The materials before and after preparation were characterized by BET and SEM. The denitration performance of the prepared catalysts for artificial flue gas were tested in a catalyst evaluation device in a temperature range of(80-280℃)and space velocity range of(32000-48000h-1). Meanwhile,the impact of SO2 and H2O on the catalyst(1/2SnFe/ATP)was investigated. The results showed that carriers might provide a large number of Brønsted acid sites,which was beneficial for the gas adsorption reaction. Among all the test catalysts,the 1/2SnFe/ATP had the best SCR denitration performance. At 200℃,the conversion of NO could reach by 96.4%. It was also found,when there was only SO2,the NO removal efficiency decreased slowly,and would still be higher than 85% if SO2 input was cut off. But when H2O and SO2 were simultaneously added,the NO removal efficiency fell sharply and would went back to above 70% if H2O and SO2 input was cut off.
    Tuned TiO2 top-porous/bottom-tubular structure for enhanced VOCs photocatalytic activity
    GU Di, ZHU Lingyue, WU Hongjun, WANG Baohui
    2016, 35(12):  3928-3933.  doi:10.16085/j.issn.1000-6613.2016.12.028
    Abstract ( 341 )   PDF (1382KB) ( 369 )  
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    The top-porous/bottom-tubular TiO2 nanotube arrays(TiO2 NTs)were prepared via a facile two-step anodization method for efficient decomposition of VOCs(volatile organic compounds)in air. The gas phase photocatalytic activity of conventional 1-step TiO2 NTs and top-porous/bottom-tubular TiO2 NTs were estimated by decomposing of methanol vapor. The results show that,a heterojunction structure formed in top-porous/bottom-tubular TiO2 NTs composite plays an important role in the dynamics of photogenerated charges. The top-porous/bottom-tubular TiO2 NTs combined structure significantly enhanced the photocatalytic activity of decomposition of VOCs,which is due to the enhanced electrons transfer and the reduce of the recombination of photogenerated electrons and holes. The mechanism for the enhancement of the photocatalytic activity of top-porous/bottom-tubular TiO2 NTs was discussed according to our experimental results.
    Preparation of MoO2/g-C3N4 catalyst and its application in the oxidation desulfurization of model oil
    XING Pengfei, LI Xiuping, JIA Baojun, ZHAO Rongxiang
    2016, 35(12):  3934-3941.  doi:10.16085/j.issn.1000-6613.2016.12.029
    Abstract ( 416 )   PDF (1660KB) ( 421 )  
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    MoO2/g-C3N4 catalysts with different MoO2 content were prepared by direct calcination of mixtures of g-C3N4 and MoO2. The structure and properties of the catalysts were characterized by XRD,FTIR,SEM,N2 adsorption-desorption. The desulfurization performance of the reaction system was investigated by using MoO2/g-C3N4 as the catalyst,H2O2 as oxidant,and ionic liquid as extractant. The effects of calcination temperature,content of MoO2,amount of hydrogen peroxide,dosage of catalyst,reaction temperature,amount of ionic liquid and the type of sulfur-containing compounds in oil,on the desulfurization efficiency were investigated. The result showed that under the optimal reaction conditions of V(H2O2)=0.2mL,m(catalyst)=0.03g,V(ILs)=1.0mL,reaction temperature 70℃ and reaction time 60min,the desulfurization efficiency of 24%-MoO2/g-C3N4 catalyst was 94.8% and the catalyst could be recycled 5 times without significant loss of activity. Furthermore,the catalytic oxidation reaction mechanism of MoO2/g-C3N4 in ionic liquid was studied in detail.
    New progress in the synthesis and application of well-defined fluorinated copolymers
    LÜ Chi, CUI Kun, YUE Chunbo, LI Shucai, MA Zhi
    2016, 35(12):  3942-3953.  doi:10.16085/j.issn.1000-6613.2016.12.030
    Abstract ( 444 )   PDF (2735KB) ( 915 )  
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    In recent years,fluorinated polymers have attracted much attention because of their excellent properties of high resistance to heat and oxygen,superior weatherability,good chemical inertness,low dielectric constants,and low surface energy,and broad application prospect in fields of hydrophobic materials,antifouling materials,surfactant,and contrast agent. Fluorinated copolymers of various topologies have been synthesized and applied in related fields. In this paper,firstly,the properties and current research status of fluorinated polymers are briefly introduced. Secondly,the new research progress of well-defined fluorinated copolymers synthesized by reversible addition-fragmentation chain transfer polymerization(RAFT),atom transfer radical polymerization(ATRP),iodine transfer radical polymerization(ITP),reverse iodine transfer polymerization(RITP),single electron transfer living radical polymerization(SET-LRP),nitroxide-mediated radical polymerization(NMP),and living anionic polymerization(LAP)are reviewed in detail respectively. In addition,the mechanism,advantage and disadvantage of polymerization,and the properties and applications of the fluorinated copolymer obtained are also summarized. Finally,the research foreground and practical application of the design and synthesis of well-defined fluorinated copolymers based on controlled/"living" polymerization are prospected. We put forward that environmentally friendly functional fluorinated polymers will be the research focuses in the future.
    Preparation of potassium chloride from K-feldspar with calcium chloride as additive agent: a review
    CHEN Jian, MA Hongwen, ZHANG Pan, LIU Meitang
    2016, 35(12):  3954-3963.  doi:10.16085/j.issn.1000-6613.2016.12.031
    Abstract ( 433 )   PDF (443KB) ( 768 )  
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    The research history and current situations of preparation of potassium chloride from K-feldspar with calcium chloride as additive agent is reviewed in this paper. Utilizing the K-feldspar derived from Baoxing county of Sichuan province as raw material,we evaluated and compared two processes of high temperature activation K-feldspar to fix carbon and hydrothermal alkaline decomposition K-feldspar from the perspectives of reaction principle,resource consumption,energy consumption,environmental compatibility and products. The results showed that both processes are feasible in principle,but the resource consumption,energy consumption and CO2 emission by calcination K-feldspar for carbon fixation process is 1.59 times,2.45 times and 4.10 times of those by hydrothermal alkaline method,respectively. The calcination K-feldspar for carbon fixation process produces KCl products as well as a large amount of hydrochloric acid and solid waste,while the hydrothermal alkaline method could completely transform the K2O,Al2O3 and SiO2 in K-feldspar of the ores into valuable products and thus maximize the utilization of K-feldspar resources,and minimize the consumption of relevant mineral resources. What's more,the calcination K-feldspar for carbon fixation process has low efficiency of carbon fixation,and the fixed carbon is even less than that discharged due to the energy consumption for fix carbon. Therefore,the calcination K-feldspar for carbon fixation process is still far from the practical engineering application.
    Preparation and application of magnetic molecularly imprinted polymer
    ZHANG Xiwen, LI Zhaozhou, LI Daomin, CHEN Xiujin, GAO Hongli, LI Zhili, CAO Li, WANG Yao, HOU Yuze, LI Songbiao, LÜ Pu
    2016, 35(12):  3964-3969.  doi:10.16085/j.issn.1000-6613.2016.12.032
    Abstract ( 457 )   PDF (546KB) ( 569 )  
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    With the features of superparamagnetism,high selectivity,high adsorption and specific recognition,magnetic molecularly imprinted polymer is synthesized by molecular imprinting technique on the magnetic particle surface. Furthermore,it is a new type of polymeric material which achieves rapid separation and directional movement in external magnetic field. This paper describes three preparation methods for magnetic particles,including physical,chemical and templating methods,and molecular imprinting technique for magnetic molecularly imprinted polymer. Additionally,this paper discusses the research progress of the three polymerizations,which are suspension polymerization,emulsion polymerization and precipitation polymerization. Finally,we summarize the applications of magnetic molecularly imprinted polymers in the analyses of pesticide residues,veterinary drug residues,heavy metal residues and biomedicine aspects. It is demonstrated that magnetic molecularly imprinted polymer has great prospects in biomedical science,especially in the treatment of antibacterial disease.
    Facile fabrication and gas separation properties of Cu-BTC/ethyl cellulose mixed matrix membranes
    LI Hao, DU Naixu, YANG Kai, DAI Yan, HE Gaohong
    2016, 35(12):  3970-3975.  doi:10.16085/j.issn.1000-6613.2016.12.033
    Abstract ( 343 )   PDF (1450KB) ( 396 )  
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    Cu-BTC,a metal-organic framework,is widely used as dispersion filler of mixed matrix membranes(MMMs)for gas separation. To accelerate the fabrication of mixed matrix membranes,the precursors of Cu-BTC were individually mixed with ethanol solution of ethyl cellulose (EC) at first and then reacted,achieving the rapid synthesis of Cu-BTC in EC. Cu-BTC/EC MMMs were fabricated accordingly,and characterized via SEM,XRD,and FTIR. The effect of EC concentration on the yield of Cu-BTC was studied,and it showed that EC had promoted the synthesis of Cu-BTC. Thermal,mechanical and gas permeation properties of the Cu-BTC/EC membranes were investigated. The CO2 permeability of MMM with 26wt% Cu-BTC was 112.3 barrer,69% more than that of pure EC,while the CO2/CH4 and CO2/N2 selectivities were almost unchanged. Moreover,the Cu-BTC/EC membranes showed higher resistance to CO2-induced swelling than pure EC membrane.
    Preparation of amino propanediol functionalized boron-chelating resins and application in adsorption of boric acid
    CHEN Shaofeng, XING Huabin, YANG Qiwei, ZHANG Zhiguo, SU Baogen, YANG Yiwen, REN Qilong, BAO Zongbi
    2016, 35(12):  3976-3984.  doi:10.16085/j.issn.1000-6613.2016.12.034
    Abstract ( 415 )   PDF (688KB) ( 242 )  
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    Two boron-chelating resins containing aliphatic 1,2-diols and 1,3-diols were prepared from porous chloromethyl polystyrene(CMPS)functionalized by 3-amino-1,2-propanediol(3-APD) and 2-amino-1,3-propanediol(2-APD),respectively. The newly synthesized resins were characterized by FTIR,EA,MIP and LPS. The FTIR spectra showed that the functional monomers were successfully grafted onto the polymer matrix. The effect of pH of boron solution,initial boric acid concentration,and foreign ions on the boron adsorption on the synthesized sorbents were studied in batch model. The maximum boron capacities of PS-3-APD and PS-2-APD could be obtained when the pH of boron solution was in the range of 9.15-9.20. Besides,the presence of foreign ions such as Na+,Mg2+,Ca2+ would deteriorate the adsorption performance due to the competitive adsorption. Kinetic studies showed that both resins adsorbed boric acid from aqueous solutions very quickly and their kinetic curves could be fitted well with pseudo second order model. Boron adsorption isotherms on both resins were better correlated with Langmuir model than with Freundlich model. The calculated maximum boron capacities of PS-3-APD and PS-2-APD by Langmuir equation were 0.730mmol/g and 0.868mmol/g,respectively. This study may offer helpful guidance in the development of novel high-performance boron adsorbents.
    Advances in research on anaplastic lympgoma kinase inhibitors
    CHEN Yalin, LI Wei, WANG Tianyang, ZHOU Xueqin, LIU Dongzhi
    2016, 35(12):  3985-3990.  doi:10.16085/j.issn.1000-6613.2016.12.035
    Abstract ( 335 )   PDF (398KB) ( 394 )  
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    Researchers have found that multiple oncogenic driver multations are closely related with the progression and prognosis of NSCLC. In the era of molecular targeted treatment,rearrangements in anaplastic lymphoma kinase(ALK)gene and echinoderm microtubule-associated protein-like 4(EML4)gene were applied in patients with non-small cell lung cancer(NSCLC). Crizotinib,an ALK inhibitor,is effective in treating advanced ALK-positive NSCLC,and the US Food and Drug Administration(FDA)approved it for treating ALK-positive NSCLC. Several mechanisms of acquired resistance to crizotinib have recently been reported. Second-generation ALK inhibitors were developed to overcome these resistance mechanisms and showed activity against ALK positive NSCLC. The latest development of crizotinib,ceritinib,alectinib etc. were reviewed.
    Electrochemical immunosensors for the detection of tumor markers
    ZHANG Haochun, LÜ Jia, ZHANG Bing, GAO Wenchao, LI Xing, CHANG Honghong, WEI Wenlong
    2016, 35(12):  3991-4000.  doi:10.16085/j.issn.1000-6613.2016.12.036
    Abstract ( 426 )   PDF (2229KB) ( 730 )  
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    Tumor is one of the severe threats to human health. The death rate of malignant can mainly reduced through early diagnosis and treatment. Therefore tumor markers are of significant clinic value in the early diagnosis. With the rapid development of nanotechnology,electrochemical sensor based on nanomatericals can make the detection of tumor markers with high sensitivity and selectivity. The protocol focused on the construction principle of electrochemical immunosensors using new nanomaterials such as carbon nanomaterials,noble metal nanoparticles,oxide nanomaterials,and quantum dot nanomaterials. It also focused on the applications of those immunosensors in the detection of alpha-fetoprotein,prostate antigen,carcinoembryonic antigen,and other tumor markers. The advantages and disadvantages of electrochemistrical sensors constructed on different nanomaterials in the detection of various tumor markers are analyzed and summarized. It is concluded that future development of the electrochemical immunosensors should be focus on miniaturization,high capacity,and commercialization of fast repoense,on-line,and real-time detection of tumor markers.
    Synthesis and application of rosin-based functional monomer
    CHEN Lijing, CAO Xiaoqin, XU Xu
    2016, 35(12):  4001-4006.  doi:10.16085/j.issn.1000-6613.2016.12.037
    Abstract ( 398 )   PDF (390KB) ( 521 )  
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    Rosin is one of the most important forestry resources in China. The main components of rosin include different resin acids. As raw material,it can take part in various reactions to synthesize functional monomers in polymer science field because of its unique chemical structures including double bond and carboxyl group. The rosin can be widely applied in painting,adhesive,aerospace,and other fields. Due to low cost,superior mechanical and thermal properties,as well as environmental friendly and renewable alternative,rosin has drawn wide public attention in polymer science field. This article reviewed the rosin-based functional monomer containing acrylate group,vinyl group,and allyl group,respectively. Its application was mainly discussed in polymer and other new material areas including polyurethane resins,epoxy resins,phenol-formaldehyde resin,organic silicone resin and unsaturated polyester. Based on the rosin-based functional monomers,a series of rosin derivatives as application of new application materials were explored,and provided new perspectives for the novel surfactants,cross-linking agents,shape memory materials and other new fields. Moreover,the prospective direction of rosin-based polymer materials was given.
    Development of hydrate anti-agglomerant based on the analysis of active components of a plant extract with anti-agglomeration effect
    WANG Xiaoqin, QIN Huibo, MA Qinglan, SUN Changyu, LIU Dameng, CHEN Guangjin
    2016, 35(12):  4007-4013.  doi:10.16085/j.issn.1000-6613.2016.12.038
    Abstract ( 387 )   PDF (572KB) ( 319 )  
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    This work provided a method for developing hydrate anti-agglomerant based on the analysis of active components of a plant extract with anti-agglomeration effect. The preliminary analysis on a plant-extract with anti-agglomeration performance demonstrated the active components mainly exist its ethyl acetate extraction section,which was proved to have the effect of preventing hydrate agglomeration by testing in a high pressure transparent sapphire cell. The Fourier Infrared Spectrometry(FTIR)and Gas Chromatography-Mass Spectrometry(GC-MS)were used to further analyze the functional group and molecular structure. Finally,a series of active materials were identified,most of which were plasticizer,emulsifier,stabilizer,and surfactant intermediate. The standard corresponding commercial materials were then purchased from commercial market and their effectiveness of preventing hydrate agglomeration was verified. Compared with the single material,the mixture of these materials performed better and could be directly used as an effective hydrate anti-agglomerant.
    Synthesis and plasticized performance of dimer acid di(2-butoxyethyl) ester
    XIE Bingxue, TAN Jihuai, HU Bin, LI Daoyu, MEI Shuqin, ZHU Xinbao
    2016, 35(12):  4014-4019.  doi:10.16085/j.issn.1000-6613.2016.12.039
    Abstract ( 332 )   PDF (601KB) ( 211 )  
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    A synthesis process of dimer acid di(2-butoxyethyl) ester from dimer acid and ethylene glycol butyl ether was studied. The process was carried out with the catalyst of tetrabutyl titanate and employed the direct esterification method. The effect of the ratio of reactants,dosage of catalyst,dehydrating agent and reaction time was investigated. The result showed that the esterification yield was 99.6%. when the molar ratio of ethylene glycol butyl ether to dimer acid was 2.5:1,the dosage of catalyst was 1.0% on the basis of the mass of dimer acid,the amount of dehydrating agent was 17.5% on the basis of the mass of dimer acid,and the reaction time was 5h. The apparent kinetics model of esterification was developed,and the equation for reaction rate is:r=9.2×105e-49.1/RTcA. The product was characterized by FTIR and 1H NMR. PVC test pieces was prepared by adding the dimer acid di(2-butoxyethyl) ester and DOP into the PVC resin separately. Dimer acid di(2-butoxyethyl) ester has good oil and water resistance and thermal stability which can be used as DOP upgrade products.
    Progress on mechanisms and influence factors of N2O production in microbial nitrogen removal process from wastewater
    CHEN Hu, WANG Ying, LÜ Yongkang
    2016, 35(12):  4020-4025.  doi:10.16085/j.issn.1000-6613.2016.12.040
    Abstract ( 425 )   PDF (360KB) ( 632 )  
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    Nitrous oxide(N2O)emitted during biological nitrogen removal process is a potent greenhouse gas and can result in the destruction of the ozone layer. This paper summarizes the mechanisms and influencing factors of N2O production during wastewater biological nitrogen removal process. Hydroxylamine oxidation and nitrifier denitrification are two main pathways to produce N2O for nitrification,and factors such as dissolved oxygen,ammonium nitrogen and nitrite mainly affect microbial activity or enzyme activity that influences indirectly N2O emission from nitrification process. Denitrification process is another important source for the production of N2O,and the quantity of N2O emission has a direct connection with nitrous oxide reductase,whose activities can be affected by factors such as dissolved oxygen,organic carbon,and nitrite. New biological nitrogen removal technologies have become potential sources of N2O,but further research on mechanisms of N2O production is needed. Although N2O emission is closely related to the changes of surrounding environment,the main cause for N2O emission is the effect of microbial actions and enzyme activities. The future research on the wastewater biological nitrogen removal process should focus on the control and reduction strategy of N2O,and shows some suggestions.
    Recent progress in disposal and recycling of spent lithium-ion batteries
    ZHANG Xiaoxiao, WANG Yangyang, LIU Yuan, WU Feng, LI Li, CHEN Renjie
    2016, 35(12):  4026-4032.  doi:10.16085/j.issn.1000-6613.2016.12.041
    Abstract ( 729 )   PDF (1886KB) ( 2454 )  
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    Currently,the fast-growing consumer electronics,electric vehicles and stationary energy storage,have spurred a surge demand for lithium-ion battery(LIB),which occupies the largest share of battery market. Accordingly,both the number and weight of spent LIBs have greatly increased. In view of their large quantities,and the environmental preservation and resources regeneration,the recycling of spent LIBs is highly desirable. In this review,we summarized the disposal and recycling processes developed in both laboratory industrial scales,especially for the research of re-synthesis of new electrode materials in the recycling process. The issues of existing recycling processes lie in the difficulties in separation and purification due to the complexity of the spent materials,secondary pollution problems and insufficient economic motivation. The research in the future should be focused on developing highly efficient,green and low-cost recycling processes.
    Research advances of pollutants degradation catalyzed by electroactive biofilm in bioelectrochemical system
    WANG Youzhao, PAN Yuan, WU Zongting, ZHOU Aijuan, ZHU Tong
    2016, 35(12):  4033-4041.  doi:10.16085/j.issn.1000-6613.2016.12.042
    Abstract ( 422 )   PDF (1569KB) ( 441 )  
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    In recent years,bioelectrochemical system(BES) which based on electroactive biofilms(EAB)is proposed as one of hot topics in environmental field for pollutants degradation of wastewater and energy recovery.According to the different roles of EABs between anode and cathode,we presented the direct and indirect electron transfer mechanisms of anode EABs with an ability of electron recovery from various pollutants'. The cathode EABs had a high diversity and specificity for catalytic reductive degradation of the refractory pollutants. Meanwhile,we also analyzed the deficiencies of EABs at the present stage,including the lower power density of electrogenesis in anode and the unclear extracellular electron transfer in cathode. These analyses indicated that the EABs community structures need to be controlled for the cooperation of different functional microbes in EABs according to the difference of actual wastewater composition,and the catalytic process of EABs can be assisted to achieve the aim of efficient pollutants removal from waste water by the pretreatment of actual wastewater or improving the electrode materials.
    Metallurgical progress of recovery indium from smelt residues
    RAO Bing, DAI Huixin, GAO Likun
    2016, 35(12):  4042-4052.  doi:10.16085/j.issn.1000-6613.2016.12.043
    Abstract ( 362 )   PDF (543KB) ( 674 )  
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    As a scarce metal,indium plays a major role in high-tech industry,which has high values in industrial application. Indium reserve is only about a sixth of the gold reserve. Without independent field,pittance of indium is mixed with lead,zinc etc. In the process of main metal smelting,indium is enriched in all kinds of smelting slag according to the physical and chemical properties. At present,many raw materials for recovering indium are the abandoned zinc smelter slag and leaching residues. Because of the complex composition of smelting waste residues,the processes to extract indium from residues have long periods and low recovery rates. According to the different treatment methods,these processes are divided into direct acid leaching and acid leaching after pretreatment. Direct acid leaching includes conventional acid leaching,hot acid leaching and oxidizing acid leaching. The pretreatment methods can be divided into two types:acid pretreatment and alkali pretreatment. The new methods and studies of enhancing the Indium leaching are mainly based on the physical methods. The conventional acid leaching is easy to be industrialized,but the recovery rate of indium is low. The hot acid leaching polluted environment. The extraction of indium from residues can be enhanced effectively by both the oxidizing acid leaching and the pretreated leaching. New laboratory studies have focused on the effects of acid leaching and various physical enhancement of Indium leaching,and have made great progress. Therefore,it is necessary to combine various methods featured with high efficiency and environment friendly in the future.
    Flue gas desulfurization research in liquid jet-absorption coupled gas cyclone-separation device
    ZHOU Xiantao, WANG Yimou, MA Liang, LIU Anlin, HE Mengya
    2016, 35(12):  4053-4059.  doi:10.16085/j.issn.1000-6613.2016.12.044
    Abstract ( 398 )   PDF (514KB) ( 334 )  
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    The traditional mist cyclone separator was improved,to possess a comprehensive function of gas-liquid injection,absorption and separation. The new type of cyclone separator was used in flue gas desulfurization experiment. The gas phase included SO2 flue gas,the liquid phase was NaOH or Na2CO3. By adjusting experimental parameters such as absorbent concentration,sulfur concentration,gas injection velocity,desulfurizer injection velocity and solid holdup to obtain the corresponding changes of the desulfurization efficiency. The results showed that the removal efficiency of SO2 increases first with the increase of the absorbent concentration,then keeps almost unchanged after the absorbent concentration reaching a certain concentration. The removal efficiency of SO2 declined with the increase of SO2 imported concentration. With the increase of imported gas velocity,the removal efficiency of SO2 also increases to a certain extent. With the increase of liquid jet speed,the removal efficiency of SO2 increases first and then tends to be unchanged to a certain degree. The best removal efficiency of SO2 can reach 85% and 73% when using NaOH and Na2CO3 as the absorbent. When the other parameters being unchanged and adding a certain amount of CaCO3 solid particles,the removal efficiency of SO2 increases 1%-2%. The liquid jet-absorption coupled gas cyclone-separation device has high desulfurization efficiency,low loss of desulfurizer. The investment and operation maintenance costs of the new type of liquid jet-absorption coupled gas cyclone-separation device were lower than flue gas desulfurization tower with the same capacity. The new type of liquid jet-absorption coupled gas cyclone-separation device has a good application prospect.
    Comparative studies on carbon dioxide emissions of typical modern coal chemical processes
    ZHANG Yuanyuan, WANG Yonggang, TIAN Yajun
    2016, 35(12):  4060-4064.  doi:10.16085/j.issn.1000-6613.2016.12.045
    Abstract ( 360 )   PDF (369KB) ( 997 )  
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    Based on the demands of the development of low-carbon economy,the CO2 emissions in several typical processes of modern coal chemical industry were analyzed in this paper,and it was put forward that scientific comparison of CO2 emissions in the processes of modern coal chemical industry should be studied. For coal-based chemicals,such as coal to olefin,coal to ethylene glycol,etc.,using CO2 emissions per unit of heat value as the evaluation index was not suitable. Based on the different characteristics of coal-based fuel products and chemicals,combining with the control target of carbon emission intensity in our country,using CO2 emissions per unit of output value and CO2 emissions per unit of industrial added value as supplementary indexes for comparative study on the level of low carbon and carbon emission intensity of different processes of modern coal chemical industry were explored. The studies showed that the results were different when using different indicators to measure the CO2 emissions of different processes of modern coal chemical industry. For coal to methanol and coal to dimethyl ether,the CO2 emissions per ton product were lower as 3.85 t and 5.0 t,respectively,but the CO2 emissions per unit of heat value were higher as 0.159 t/GJ and 0.160 t/GJ,respectively. Under the crude oil price system of 80$/bbl and 40$/bbl,the CO2 emissions per unit of output value and industrial added value of coal-based synthetic natural gas and coal to methanol were both higher than other modern coal chemical products.
    Temperature programmed desorption(TPD)studies on the effect of flue gas component on mercury adsorption
    CHEN Mingming, DUAN Yufeng, ZHOU Qiang, LIU Shuai, DING Weike, LIU Meng
    2016, 35(12):  4065-4071.  doi:10.16085/j.issn.1000-6613.2016.12.046
    Abstract ( 314 )   PDF (499KB) ( 707 )  
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    Removing mercury technology of activated carbon in flue gases is very mature. However, the mechanism of the mercury reaction is seldom.Experiments on mercury capture by a commercial activated carbon and a 1% NH4Br-modified activated carbon were carried out in a fixed-bed reactor under simulated flue gas to study the reaction path among the mercury,flue gas and activated carbon. The effect of single component such as O2,CO2,SO2 and NO was investigated. Then the temperature programmed desorption technique was used to identify the mercury species on the adsorption products. The results showed that the bromine impregnation on the activated carbon has a great promotion on the mercury capture. O2 and CO2 play a positive role in the mercury capture process,while the SO2 plays a negative function. According to the TPD analysis results,NO promotes mercury capture significantly because of the formation Hg2(NO3)2 on the activated carbon surface. The elemental mercury was oxidized to generate HgO when O2 was injected.SO2 competed with Hg0 on the surface functional groups of activated carbon and HgS was formed because of C-S was formed to react with Hg0.CO2 has little effect on the adsorption mechanism of NBAC.
    The effect of lignin in bagasse enzyme hydrolysis
    XIAO Fang, QIN Yimin, LIU Youyan
    2016, 35(12):  4072-4075.  doi:10.16085/j.issn.1000-6613.2016.12.047
    Abstract ( 327 )   PDF (3173KB) ( 527 )  
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    The mechanical activation method was employed to process bagasse. The effect of lignin on enzymatic hydrolysis was studied effect when the raw material accessibility changed. The X-ray diffraction and scanning electron microscopy(SEM)were used to determine the crystal structure and surface morphology of bagasse,to characterize the raw material accessibility,and analyze the influence of the possible mechanisms. The results showed that the effect of lignin on bagasse enzyme hydrolysis was related to bagasse accessibility. The higher raw material availability was,the smaller the effect was. When the accessibility of bagasse was relatively low,lignin affected the rate of enzymatic hydrolysis of bagasse in two ways (limiting cellulose accessibility and unproductive binding of the enzymes) simultaneously. When the availability of raw material increased to a certain level (for example,2 hours by mechanical activation of bagasse) and lignin adsorption of cellulose was virtually eliminated. The main effect of Lignin on bagasse enzymatic hydrolysis was limiting enzyme accessibility.
    Treatment of methylene blue wastewater with a compound photo-catalyst TiO2-HNTs combined with dielectric barrier discharge
    YU Fang, CHEN Yuantao, ZHANG Wei, HE Wenfang, WANG Yunsheng, LIU Chen
    2016, 35(12):  4076-4081.  doi:10.16085/j.issn.1000-6613.2016.12.048
    Abstract ( 310 )   PDF (540KB) ( 388 )  
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    In order to further improve methylene blue (MB) removal efficiency,a method of discharge plasma combined with photo-catalyst was adopted in this research. A compound photo-catalyst(TiO2-HNTs) was made by a sol-gel process,which was characterized by XRD,FTIR and GTA. Photo-catalytic ability and influencing factors were tested. The kinetics of the reaction was studied. The results showed that TiO2-HNTs has a synergetic effect when combined with dielectric barrier discharge,and significantly increases methylene blue removal rate. The removal rate of methylene blue was 85.37% after a 60 minutes reaction. The degradation of methylene blue is in accordance with the apparent pseudo-second-order. The degradation of methylene blue is influenced by many factors,including MB concentration,TiO2-HNTs concentrations,calcination temperature,discharge power and air flow. The degradation is optimal when MB concentration is 100mg/L,TiO2-HNTs concentrations is 70mg/L,calcination temperature is 300℃,discharge power is 200W and air flow is 200mL/min.
    Separation of methanol and dimethyl carbonate azeotrope by extractive distillation using ionic liquid as solvent
    LI Jun, HE Wenjun, QI Zhiwen, ZONG Hongyuan, YANG Weimin
    2016, 35(12):  4082-4087.  doi:10.16085/j.issn.1000-6613.2016.12.049
    Abstract ( 387 )   PDF (481KB) ( 807 )  
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    Focused on separation of methanol(MEOH)and dimethyl-carbonate(DMC)azeotrope,the extractive distillation process employing ionic liquid 1-octyl-3-methylimidazolium tetrafluoroborate([omim] [BF4]) as solvent was designed and simulated based on Aspen Plus. To verify the reliability of simulation results,binary interaction parameters were correlated by NRTL using vapor-liquid equilibrium data. The flow rate of[omim] [BF4],reflux ratio,feed stage and operation conditions of flash tower were optimized to obtain MeOH and DMC with purity above 99.5%,respectively. Compared to the dimethyl oxalate(DMO)process,[omim] [BF4] process presents lower requirements for towers,lower solvent and energy consumption. Economy analysis indicates that the column cost and packing cost of[omim] [BF4] only account for 78% and 37% of DMO process respectively,while the energy consumption increase 4% and solvent cost is 6.5 times higher than DMO process. As a result,the total annual cost of[omim] [BF4] is comparable with DMO process. Hence,the[omim] [BF4] process shows application potential in MeOH and DMC separation.
    Techno-economic comparison of the thermodynamic system at lignite-fired boiler's cold-end for recovering waste heat of exhaust gases
    MA Youfu, YANG Lijuan
    2016, 35(12):  4088-4095.  doi:10.16085/j.issn.1000-6613.2016.12.050
    Abstract ( 312 )   PDF (628KB) ( 494 )  
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    It is an important way to increase the efficiency of a thermal power plant by recovering the waste exhaust gas heat at boiler cold-end with a stepwise integration with the heat regenerative system of steam turbines. In this paper,an in-service 600MW lignite-fired supercritical power unit was used as a reference unit to calculate and compare the thermal economy and techno-economic performances of three kinds of typical heat recovery processes at boiler cold-ends:low-temperature economizer,segmented air heating and bypass flue. The results showed that,with the recovery of boiler exhaust heat from 148℃ to 90℃,the three above-mentioned processes can make the net standard coal consumption rate reduced by 4.43g/(kW·h),5.84g/(kW·h) and 6.48g/(kW·h),respectively. Meanwhile,25.62 million CNY,23.48 million CNY and 22.61 million CNY are needed as the initial costs of the three heat recovery projects. If the 600MW unit runs 5500 hours per year with the rated load,the three processes can annually increase the earning of the unit by 9.94 million CNY,13.50 million CNY and 15.14 million CNY from coal savings,meaning that their dynamic payback periods are 3.12 years,2.00 years and 1.71 years,respectively. Those results indicate that the efficiency of a lignite-fired power unit can be significantly increased via an exhaust heat recovery process. Among the three processes,the bypass flue process shows the best thermal economy and techno-economic performance,therefore,it is recommended for preferential applications.
    Coal direct conversion to high quality liquid fuels and chemicals
    HU Haoquan
    2016, 35(12):  4096-4098. 
    Abstract ( 312 )   PDF (297KB) ( 578 )  
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    The background,research status,research tasks and goals of the National Key Research and Development Project "Basic research on low rank coal direct conversion to high quality liquid fuels and chemicals" were introduced in this paper. The researches were expected to make a great progress in further understanding the mineral characteristics and weak bonding structure of low rank coal and mechanism of free radical reactions;clarifying the direct conversion process approach,product controlling mechanism and directional catalytic conversion principles;constructing new coal pyrolysis reactor for high quality and high yield of oil and gas,new coal hydrogenation liquefaction technology for rich aromatics production,and new technology of coal liquid product to high performance jet fuel and chemicals,etc.,thus to improve the technology system for low rank coal directly into high quality liquid fuels and chemicals.
    Key technologies study and application demonstration of near-zero-liquid-discharge and resource recovery of coal chemical industry wastewater
    JIANG Zhongyi, LI Yuping, CHEN Zhiqiang, HAO Hongxun, LIU Jianzhong, HAN Hongjun
    2016, 35(12):  4099-4100. 
    Abstract ( 370 )   PDF (286KB) ( 999 )  
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    In this paper,the research background,general idea,main contents,technology roadmap and expected outcomes of a National Key Research and Development Project "Key technologies study and application demonstration of near-zero-liquid-discharge and resource recovery of coal chemical industry wastewater" are briefly introduced. Hopefully,through this project,the common key technologies with "4-high"(high pollutant removal,high water recycling,high resource recovery and high technical stability)and "2-low"(low treatment cost,low investment cost)features will be established,the whole chain technology innovation system related to treatment,reclamation and resource recovery of coal chemical industry wastewater will be constructed,and the technology framework for the optimal combination of long-process-flow and short-process-flow treatment will be formed.
    Key technologies and application of producing basic chemical materials from low-rank coal
    REN Qilong
    2016, 35(12):  4101-4102. 
    Abstract ( 330 )   PDF (303KB) ( 360 )  
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    The production of basic chemical materials including calcium carbide and acetylene is an important approach to realizing the value-added conversion of low-rank coal. However,current production technologies usually suffer from many problems including severe pollution,large energy consumption and high cost. This project is intended to reveal the basic science in the processes of mass transfer and chemical conversion under the extreme conditions in an electric field-coupling reaction system,and give deep understanding of the principles of process control,scaling-up and energy recovery. Then,many key technologies in the production are expected to be greatly improved,including the technology of industrializing the rotating arc plasma torch,the power supply with large current for hydrogen plasma and the arc starting at low voltage,the design of long-life electrode and the ablative compensation technology,the low-cost molding of powdery raw materials and the high-temperature transportation of materials. Based on these achievements,a highly efficient,energy-saving and low-cost process for the production of calcium carbide and acetylene from low-rank coal will be developed,and a 5000t/a demonstration plant of producing acetylene from coal by plasma pyrolysis and a 800000t/a industrial plant of the regenerative production of calcium carbide will be established.
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