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Table of Content
05 February 2018, Volume 37 Issue 02
    Nickel based ethanol steam reforming catalysts: mechanism, deactivation and structure-activity relationship
    ZHAO Huabo, LI Min, LUO Gang
    2018, 37(02):  419-428.  doi:10.16085/j.issn.1000-6613.2017-0962
    Abstract ( 335 )   PDF (412KB) ( 828 )  
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    According to the trend of hydrogen utilization, ethanol steam reforming reaction (ESR) have attracted more and more research interest. Nickel based ESR catalyst exhibits great potential for industrial application due to its high activity, selectivity and low cost. Nevertheless, there is still room for enhancing its stability, lowering the reaction temperature and increasing the yield of hydrogen. Comprehensive understanding of the reaction mechanism, deactivation mechanism and activitystructure relationship is necessary for preparing more efficient catalysts. Herein, the research progress of nickel based ESR catalyst has been reviewed. Firstly, new insights into reaction mechanism based on results of in-situ spectroscopy, kinetic analysis and theoretical calculation was introduced. Next, the reason for ESR catalyst deactivation was elucidated. Then we discussed the deactivation, active phase, size effect, promoter effect and bimetallic effect issues. Finally, the progress of novel catalysts arisen with the fundamental researches mentioned above was summarized in brief. Our perspective on the future development of nickel based ESR catalysts were presented. The operando/in-situ characterization methods are believed to bring in new understanding of the reaction mechanism and structure-activity relationship of nickel based catalysts, while the application of novel materials, such as molybdenum carbide, may prompt the catalytic properties of nickel based catalysts.
    Injecting pattern defects and improvements of static gas wave refrigerator
    ZOU Jiupeng, LIU Xuewu, XU Weihua, LI Junlong
    2018, 37(02):  429-436.  doi:10.16085/j.issn.1000-6613.2017-0897
    Abstract ( 298 )   PDF (950KB) ( 494 )  
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    In this study, it was found and confirmed one important reason for the low efficiency of static gas wave refrigerator by swing oscillation distributing gas injection. Because the periods and injection durations in every gas wave tubes are all not equal, the expansion ratio of the tubes located in both sides are decreased, very small load of the tubes located in intermediate region, and gas injection alternating fast and slow of each tubes deviated from the middle. These result in every gas wave tubes are not effective adequately. Refrigeration efficiency of each gas wave tubes located in different regions were calculated by computational fluid dynamics, and were compared with efficiency of the ideal injection pattern, so the restriction degree and growth potential of efficiency were exposed. Simulation showed that ideal 1/4 duty ratio pulse injection may improve relative value of efficiency about 45%, and that of 1/8 close to 70% comparing with that of the actual 1/2 duty ratio pattern. By the single tube model machine experiments, the refrigeration efficiency of same tube corresponding to different duty ratio gas injection modes were measured and compared. The results showed that the growth trend along with the decrease of the gas injection duty radio, and injection frequency corresponding to efficiency peak valley point, were consistent with the simulation results. For every gas wave tubes of the static gas wave refrigerator to efficient refrigeration, two kinds of novel and efficient wall oscillators that may distribute gas injection for four tubes with equal 1/4 duty ratio and equal cycle were recommended. Mechanisms and performances of the new type two-stage wall oscillator were also introduced succinctly.
    Distribution characteristics of salting-out particles on the surface of steam rotor blade based on population balance model(PBM)
    HU Pengfei, LI Yong, CAO Lihua, WU Xuefei
    2018, 37(02):  437-443.  doi:10.16085/j.issn.1000-6613.2017-1765
    Abstract ( 235 )   PDF (12722KB) ( 159 )  
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    In order to get a better understanding of microscopic behavior of salting-out particles in a steam turbine, a high-pressure grade rotor blade was employed in a supercritical steam turbine as a research object and the distribution of salting-out particles in the flow field from a steam turbine rotor blade was simulated using CFD-PBM method. The diameter distribution of salting-out particles in a rotor blade and the number density distribution of salting-out particles in the tailed-edge area of rotor blade with different load situations were obtained. The simulation results showed that the salting-out particle diameter near the suction side was smaller than that near the pressure side in a steam turbine rotor blade, and the salting-out particle diameter at the blade bottom was smaller than that at the blade tip. The particle number density distribution law at the pressure side of rotor blade was presented that the particle number density was larger both at the leading edge and at the tailed-edge of rotor blade while the particle number density was smaller in the middle parts of rotor blade, and the maximum value of salting-out particle number density distribution did not appear in the position having the maximum component number and particle diameter in the rotor blade, but it appeared in the position where salting-out particles with the average diameter 110-150μm deposit. When steam turbine was under 30% load operation, the number density of salting-out particles with 40μm diameter was 1.5 times than the situation when steam turbine was under rated load operation, while the number density of salting-out particles with 140μm diameter was only 80% of the situation when steam turbine was under rated load operation.
    AHP-SDG model establishment and key node identification of chemical process system based on complex network
    JIANG Ying, WANG Zheng, QIN Yan, YUAN Jianbao, JIA Xiaoping, WANG Fang
    2018, 37(02):  444-451.  doi:10.16085/j.issn.1000-6613.2017-0985
    Abstract ( 258 )   PDF (775KB) ( 590 )  
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    A method of establishing AHP(analytic hierarchy process) -SDG(signed directed graph) model and identifying key nodes was proposed based on complex network. Considering high complexity, poor resolution and some variables neglected in the modeling of chemical process system. Firstly, system SDG model was established and transformed into undirected network after dividing hierarchy structure of chemical process. According to the multi-attribute decision-making method, the subsystems, which contain the key node, were identified by selecting multiple node importance indices, such as degree centrality, closeness centrality, flow betweenness centrality, eigenvector centrality and structural holes. The weight of each index was calculated by principal component analysis. Secondly, the subsystem SDG model was transformed into directed network. Key nodes were found further through LeaderRank algorithm. Experimental results showed that this method can not only reduce the complexity of modeling, but also can improve the comprehensive and accuracy of identification. Thereby, it can improve the security and stability of chemical process.
    Characteristic for high temperature corrosion of water wall tube under gas-solid phase sulfur
    WANG Jian, HUANG Yaji, ZOU Lei, YUE Junfeng, XU Ligang, YANG Zhao, ZHA Jianrui, XIA Wenqing
    2018, 37(02):  452-458.  doi:10.16085/j.issn.1000-6613.2017-0913
    Abstract ( 196 )   PDF (634KB) ( 241 )  
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    The high temperature corrosion experiments of power plant boiler water wall tube materials (12Cr1MoVG and 15CrMoG) have been made using the test bed-high temperature tube furnace. Corrosion mass gain method was used to gain the corrosion kinetics curve under gas phase sulfur and gas-solid phase sulfur. Furthermore, the micromorphology and element contents of corrosion test block were analyzed by SEM and EDS. The results showed that the corrosion kinetics of 12Cr1MoVG and 15CrMoG can be described by the double logarithmic equation. The corrosivity of interaction conditions was much stronger than that of gaseous S. The corrosion resistance of 15CrMoG was superior than that of 12Cr1MoVG. It is revealed that the corrosion layer can be roughly divided into three layers, namely, stripping blade layer, transition layer and corrosion permeability layer. When exposed to the condition of gas phase sulfur, the corrosion layer is thick and compact. When exposed to the interaction conditions of gas phase sulfur and solid phase sulfur, the corrosion layer is thin, brittle and easy to spall. In addition, the concentration of sulfur is present in the corrosion layer, and the sulfur mass fraction in corrosion permeability layer is as high as 6.65%. The oxygen content increases from the surface of the metal substrate to the surface of the corrosion layer.
    Analysis of structural heat transfer characteristics of vertical magnesium reduction tank in reduction process
    XU Qian, FENG Junxiao, ZHOU Jingzhi
    2018, 37(02):  459-467.  doi:10.16085/j.issn.1000-6613.2017-0999
    Abstract ( 243 )   PDF (624KB) ( 340 )  
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    In this paper, in order to solve the problem of large consumption and short life of magnesium reduction tank, the bearing capacity of the vertical magnesium reduction tank was studied with respect to temperature, number of fixed end, length and thickness of tank taking into account to the present situation of reduction process of magnesium metal at home and abroad. Finite element method was used by ANSYS software to simulate the reduction process, tank body temperature and stress fields of the reduction system. Structure characteristics and buckling stress limit of the vertical magnesium reduction tank were studied. The influence of the material volume strength of tanks was considered at the same time to figure out the rules between material volume and temperature field, and the buckling stress limit of the reduction tank. Results showed that the large difference of heating rate between the center and edge of material was affected by the conduction of material layer and endothermic of reduction reaction. The existence of the central tube could reduce the reduction period of the magnesium tank properly, which had little influence on the reduction reaction of magnesium. The high temperature load could reduce the buckling stress of the reduction tank by more than 20%, and has little effect on the deformation. Therefore, the working temperature of the reduction tank should be reduced as much as possible.
    Process simulation of synthesis of ethyl acetate by reactive distillation catalyzed by ionic liquid
    DONG Yanbo, HE Ruining, MU Chunxia, ZOU Yun, TONG Zhangfa
    2018, 37(02):  468-474.  doi:10.16085/j.issn.1000-6613.2017-0719
    Abstract ( 337 )   PDF (443KB) ( 865 )  
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    In order to study the effect of ionic liquid in reactive distillation, the synthetic process of ethyl acetate by reactive distillation was simulated using ionic liquid 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM]HSO4) as catalyst. On the basis of the obtained parameters of esterification reaction kinetics, the reaction distillation process was established with Aspen Plus software. The effects of catalyst dosage, distillation plate number, reaction plate number, feed position, feed molar ratio, liquid holdup and reflux ratio on reactive distillation process were investigated. It was found that the mass fraction of ethyl acetate at the top of the column increased with the increase of catalyst dosage, distillation plate number, reaction plate number and trays liquid holdup. The process had the optimum reflux ratio and feed molar ratio. The optimized conditions were as follows:the molar ratio of ionic liquid to acetate acid of 1:2.5, the molar ratio for acetate acid to ethanol of 4:1, the theoretical plate number of 21, the 7th plate for feeding the acetic acid and catalyst, the 19th plate for feeding the ethanol, the trays liquid holdup of 0.1L and the reflux ratio of 4. Under the optimized conditions, the mass fraction of ethyl acetate at the top of the column was 98.73%。
    Discussion and analysis of application of bypass pigging technology
    CHEN Jianheng, LUO Xiaoming, HE Limin, LI Xiaowei, LI Qingping, YAO Haiyuan
    2018, 37(02):  475-484.  doi:10.16085/j.issn.1000-6613.2017-0904
    Abstract ( 338 )   PDF (2142KB) ( 768 )  
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    For the purpose of discussing and analyzing the application of bypass pigging technology, the key parameters which have significant influence on the pig motion were analyzed by establishing the bypass pigging model through force analysis on the pig. Counter measures of eliminating the bypass pigging risks were put forward by discussing certain engineering applications. The study showed that the key parameters of bypass pigging technology included pressure loss coefficient, bypass fraction and friction between pig cups and pipe walls. The pressure loss coefficient which was the function of pig structural parameters reflected the contribution of the bypass port to the pressure drop. The pressure loss coefficient for a bypass pig with a structure of a conventional bypass port, or a deflector in the front, or an internal valve can be calculated by summing the proportion of different parts in the pig linearly. Optimizing the size of bypass fraction for a specific field condition was the core of bypass pigging technology. The variation of pig velocity in different bypass fractions turned out to be nonlinear and the pig's stick-slip behaviors intensified with the increase of bypass fraction. The effects of liquid lubrication on the reduction of the friction were always neglected by current researches which also failed to couple the variation of friction along the pigging process. Finally, the future development trend was prospected. The study on the variation of friction along the pigging process and pressure loss coefficient of a structure with an internal valve was of great significance for optimizing the bypass pigging model. Coupling the connection among bypass fraction, pig velocity and transport of liquid loading will be the future hot research topic.
    Optimization of grape seed oil extracted with supercritical carbon dioxide
    ZONG Jianjun, LIAO Chuanhua
    2018, 37(02):  485-491.  doi:10.16085/j.issn.1000-6613.2017-0944
    Abstract ( 325 )   PDF (516KB) ( 530 )  
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    To recycle the valuable by product of the wine industry, supercritical carbon dioxide (CO2) extraction was used to extract oil with unsaturated fatty acids from the grape seeds. The goal was to test the extraction of grape seed oil by the supercritical CO2 extraction technique. Single parameter experiments were designed to investigate the influence of extraction pressure, extraction temperature, CO2 flow rate, and residence time. The extraction pressure was the main factor to affect the extraction yield. The optimal values of extraction temperature and CO2 flow rate for the extraction yield of grape seed oil were obtained. The response surface experiments were designed based on the result of single parameter experiments. Central composite design(CCD) was chosen to find the optimal conditions for the extraction of grape seed oil. The multivariate regression equation was established and the variance analysis was carried out, The model P-value is less than 0.0001. At the optimal extraction conditions:28MPa for extraction pressure, 321K for extraction temperature, 15.5L/h for CO2 flow rate, and 155 min for residence time, the extraction yield of 14.12% was achived.
    Purification of N-vinylpyrrolidone by crystallization
    SU Ao, LI Sifang
    2018, 37(02):  492-496.  doi:10.16085/j.issn.1000-6613.2017-0990
    Abstract ( 369 )   PDF (353KB) ( 315 )  
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    For the polymers of N-vinylpyrrolidone used in food and pharmaceutical fields, a purity of the N-vinylpyrrolidone monomer higher than 99.9% is required. However, it is often very difficult to meet the requirement by fractional distillation. To solve this problem, a crystallization process was applied to purify N-vinylpyrrolidone from industrial grade (99.5%) to pharmaceutical grade (99.9%). The effects of crystal seed addition amount, temperature of adding crystal seed, cooling rate, final crystallization temperature, crystallization time, heating rate, final sweating temperature, and sweating time on the purity and yield of the product were investigated. The appropriate operating conditions were obtained as follows:crystal seed addition amount is of 0.1% based on the weight of raw material, temperature of adding crystal seed of 11℃, cooling rate of 6℃/h, final crystallization temperature of 6℃, crystallization time of 20 min, heating rate of 6~8℃/h, final sweating temperature of 12℃, and sweating time of 30min. N-vinylpyrrolidone of industrial grade(99.5%) can be purified through single-stage crystallization to a purity more than 99.95% with a yield more than 74.5%. Compared to other separation methods, this method has obvious advantages.
    Research advance in biomass steam gasification for hydrogen-rich syngas and its application
    JIA Shuang, YING Hao, SUN Yunjuan, SUN Ning, XU Wei, XU Yu, NING Siyun
    2018, 37(02):  497-504.  doi:10.16085/j.issn.1000-6613.2017-0963
    Abstract ( 495 )   PDF (369KB) ( 1199 )  
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    Biomass steam gasification is an efficient thermochemical process, and it can converts raw materials to hydrogen-rich syngas which can be applied widely. It has potential to substitute fossil fuels to produce hydrogen. Different biomasses greatly affect the gasification and hydrogen production capacity. The choice of feedstocks is crucial for gasification to produce hydrogen-rich syngas. In addition, the adjustment of operation parameters including reaction temperature, steam flow rate, catalyst and adsorbent can optimize the quality of syngas and enhance hydrogen concentration. In this paper, the effect of operation conditions on biomass steam gasification for hydrogen-rich syngas was reviewed. Meantime, the research status of bio-char gasification for hydrogen-rich syngas was discussed. High quality of hydrogen-rich syngas can be produced by char gasification, which is kinetically limitation, thus this process requires catalyst to improve char reaction rate. It was also introduced the catalytic mechanism of potassium salts. The prospect of hydrogen-rich syngas application was proposed, including high purity hydrogen for fuel cell and synthetic natural gas.
    Research progress of hydrate formation induction time
    YONG Yu, SHI Bohui, DING Lin, LI Wenqing, LIU Yang, SONG Shangfei, GONG Jing
    2018, 37(02):  505-516.  doi:10.16085/j.issn.1000-6613.2017-1006
    Abstract ( 492 )   PDF (644KB) ( 865 )  
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    The induction time of hydrate formation is an important parameter for the characterization of hydrate formation process, the research of which is of great significance for controlling of hydrate risk and application of hydrate technology. In this paper, the researches of hydrate formation induction time in recent years were reviewed from four aspects including the research methods, hydrate guest gas types, research contents and the induction time distribution. The results showed that it mainly revolved around two aspects including the analysis of qualitative influencing factors and the establishment of quantitative characterization models. The main qualitative factors influencing the induction time and their influence on the induction time were summarized. The establishment process and applicable scope of the quantitative characterization models were analyzed. Overall, the research and analysis of qualitative influencing factors of hydrate formation induction time were relatively unsystematic and a further study on hydrate formation and nucleation mechanism from the micro perspective was needed, while the existing quantitative characterization models were only applicable for the prediction of induction time in specific conditions. At last, the future research suggestions for hydrate formation induction time were proposed.
    Advances in carbon dioxide hydrate kinetic additives
    SUN Xian, LIU Dejun
    2018, 37(02):  517-524.  doi:10.16085/j.issn.1000-6613.2017-0987
    Abstract ( 376 )   PDF (540KB) ( 612 )  
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    It is a hot topic to capture carbon dioxide by forming hydrate. However its application is limited due to the harsh formation conditions of carbon dioxide hydrate and low yield rate of hydrate. Using additives can improve hydrate separation effect. The advances in carbon dioxide hydrate kinetic additives at home and abroad were introduced and analyzed from two aspects, the enhancement of kinetic additives on carbon dioxide hydrate generation and the mechanism of additives promoting carbon dioxide formation. For the enhancement of kinetic additives, the effects of different types of kinetic additives on hydrate formation and the inhibitory effect on hydrate formation at high concentrations were discussed. In terms of the mechanism of additives promoting carbon dioxide formation, the recent research results were summarized and the shortcomings of the mechanism were pointed out. In addition, the lack of carbon dioxide hydrate kinetic additives and the future development of future researches were also discussed. The relationship between the effect of kinetic additives on hydrate formation and its containing groups needs to be further studied; secondly, there is no unified conclusion about the mechanism of hydrate formation by kinetic additives, which may be due to the fact that the current study focuses on the change in the external form of the hydrate and does not explore the change in the internal structure of the hydrate, so the effect of additives on the hydrate internal structure changes needs to be further studied.
    Optimization of culture technology of Chlorella vulgaris in airlift reactors with internal light source
    ZHANG Fenfen, MA Xiaojian, FANG Shuqi, BAI Jing, CHANG Chun
    2018, 37(02):  525-532.  doi:10.16085/j.issn.1000-6613.2017-0859
    Abstract ( 282 )   PDF (4698KB) ( 539 )  
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    To explore the optimal cultivation conditions of Chlorella vulagris in the airlift photo-bioreactor, a custom-designed 50 L airlift reactor with an internal light source was developed, and the influence of light wavelength, intensity of light source, light and dark cycles and supply of carbon dioxide on the growth of Chlorella vulagris were investigated in this study. Single factor experiments were firstly conducted with algae cell density as the investigation index. Based on that, the response surface methodology was further adapted to optimize the process conditions. The optimal conditions were as follows:red-blue lights as light source, 9615 lux of light intensity, 17.5h:6.5h of light-dark cycles and 30L/h of carbon dioxide ventilation. Under the optimal conditions, three verification experiments were performed. After 15 days cultivation, the harvested cell density of Chlorella vulagris was 5.48×107 cells/mL, which was close to the results predicted, and the dry weight was 1.21 g/L, increased by 157%. These results can provide an important reference for the application of internal light source airlift reactor in microalgae culture.
    Effects of operating conditions on PEMFC dynamic behavior by EIS
    HE Li, HAN Zhe, FENG Kun, NIU Zhuo, LIU Youxian, LIU Zhixiang
    2018, 37(02):  533-539.  doi:10.16085/j.issn.1000-6613.2017-0852
    Abstract ( 378 )   PDF (490KB) ( 969 )  
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    In this paper, the effect of four operating conditions on the electrochemical impedance of the proton exchange membrane fuel cell(PEMFC) was investigated by using the electrochemical impedance spectroscopy (EIS), which included temperature, humidity, cathode and anode stoichiometry. The compound resistance-capacitance parallel equivalent circuit was used to fit the experimental results. The experimental results showed that the high frequency impedance of cathode stoichiometry affected PEMFC single cell most, followed by the temperature, humidification temperature, and anode stoichiometry when the current density of PEMFC single cell was 1400mA/cm2.The influence of different operating conditions on the ohmic impedance in high frequency impedance spectrum was not obvious, which mainly changed the output performance of the PEMFC cell by affecting the anode and cathode faraday impedance. The equivalent results and the experimental results showed consistent changing rule of impedance in different frequency bands, the varaition of each impedance can be controlled within 2mΩ, which can effectively replace the experimental results.
    Experimental research on mercury removal by modified petroleum coke with SO2 activation
    LI Jiachen, YIN Qi, WANG Chenping, CHEN Mingming, DAI Ling, ZHANG Yun, DUAN Yufeng
    2018, 37(02):  540-545.  doi:10.16085/j.issn.1000-6613.2017-0834
    Abstract ( 262 )   PDF (436KB) ( 468 )  
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    Three different crude high sulfur petroleum cokes were activated with SO2 to prepare samples of the petroleum coke with high sulfur content. The physical and chemical properties of the samples were characterized using surface area and porosity analyzer, X-ray photoelectron spectroscopy and ultimate analysis. Experimental studies on mercury removal were investigated in a fixed bed reactor system. The results showed that the process of modification of petroleum coke with SO2 effectively loaded sulfur on the surface. A large amount of organic sulfur(thiophene) was detected on the surface of the high-sulfur-content petroleum coke, which indicated its great ability of mercury removal. The sulfur content and sulfur formd on the surface of petroleum coke with high sulfur content have a great influence on the mercury removal capacity. The microstructure and micro morphology on surface of the petroleum coke played a remarkable role on mercury removal ability. The Hg0 penetration rate decreased and the mercury removal ability of high-sulfur-content petroleum coke increased with reduction of adsorption temperature in a certain range.
    Experiment on attapulgite for CO2 hydrate formation kinetics
    YU Dongmei, CHEN Shuo, WANG Shuli, RAO Yongchao, LÜ Xiaofang
    2018, 37(02):  546-553.  doi:10.16085/j.issn.1000-6613.2017-0869
    Abstract ( 275 )   PDF (572KB) ( 586 )  
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    CO2 hydrate is often formed in oil and gas production, storage and transportation, and CO2 transporting via pipelines. The most effective method to prevent CO2 hydrate is to add inhibitor. To solve the problem of CO2 hydrate blockage, the effects of ultrasonic processing attapulgite, as a hydrate inhibitor,(mass concentration of 0, 0.05mg/mL, 0.30mg/mL, 0.50mg/mL, 0.75mg/mL, 1.00mg/mL and 1.50mg/mL) on the kinetics of CO2 hydrate formation were investigated by using the high-pressure reactor. The experiments were conducted at temperatures 2℃ and initial cell pressures 3MPa. The impacts of various concentrations of attapulgite on CO2 hydrate formation were studied. The induction time and the generated quantity were measured by changing pressure. The production of hydrate was calculated by the kinetic model. Furthermore, the microscopic mechanism of inhibiting hydrate formation was analyzed. The results showed that the suspension of attapulgite had significant effect on inhibiting the formation of hydrate. The optimal concentration is 0.75mg/mL. Compared with the formation experiment of CO2 hydrate in deionized water, the induction time increased by 200%; the hydrate formation would be reduced in the attapulgite system, which can be decreased by 12.8% at the optimal concentration of 1.5mg/mL. The inhibition mechanism of attapulgite is mainly due to its selective adsorption and blocking mass and heat transfer. Therefore, the attapulgite, as a new CO2 hydrate inhibitor, has a good inhibitory effect as well as economy and environmental friendly.
    Modeling and heat integration for water gas shift unit of coal to SNG process
    XIAO Honghua, LIU Yang, HUANG Hong, YANG Siyu
    2018, 37(02):  554-560.  doi:10.16085/j.issn.1000-6613.2017-0828
    Abstract ( 268 )   PDF (394KB) ( 614 )  
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    Technologies of coal to synthetic natural gas(SNG) project have made a breakthrough after further upgrade demonstration in the 12th Five-Year period of China. However, SNG projects suffer from relatively low degree of integration and high energy consumption. High-efficiency recovery and utilization of the reaction heat of the water gas shift(WGS) unit are efficient ways to reduce energy consumption. A fixed-bed reactor model based on reaction kinetics was established. Under the condition of meeting requirement of H2/CO ratio, system exergy output was improved by optimizing the reaction operating parameters. A new heat-recovery network was established based on the energy analysis of the optimized process. Optimization of reaction parameters and integrated optimization of heat exchanger networks were realized. In comparison to the present technology, the energy efficiency of the new process increased by 9%, reaching 86.3%. Investment enhanced by 5.5% and the payback period was 2.1 years.
    Numerical simulation of pipeline hydrate slurry flow behavior based on population balance theory
    SONG Guangchun, LI Yuxing, WANG Wuchang, JIANG Kai, SHI Zhengzhuo, YAO Shupeng
    2018, 37(02):  561-568.  doi:10.16085/j.issn.1000-6613.2017-0787
    Abstract ( 248 )   PDF (11850KB) ( 169 )  
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    The flow behavior of hydrate slurry is of great importance to assurance of deep sea pipeline flow and industrial popularization of gas storage and transportation using hydrating method. However, the present methods of simulation of hydrate slurry flow behavior are limited and need improvements. Therefore, a population balance model based on the dynamics of hydrate particle agglomeration was introduced. The model concentrated on the collision frequency, agglomeration efficiency, breakage frequency and particle size distribution of the broken flowing hydrate particles and could well describe the hydrate slurry flow behavior. A three-dimensional geometric model was built according to an experimental setup in the literature and then the population balance model together with several relevant solid-liquid two-phase flow models was solved using software Fluent 14.5. In this way, the influences of flow rate and hydrate volume fraction on hydrate volume concentration distribution, hydrate particle size distribution and pressure drop were simulated. The simulation results were in good agreement with the experimental results in literature and could provide references for the application of hydrate slurry technology.
    Research progress of mesopore-modification of Y zeolites
    LIU Yujie, YAN Lunjing, BAI Yonghui, LI Fan
    2018, 37(02):  569-575.  doi:10.16085/j.issn.1000-6613.2017-0830
    Abstract ( 394 )   PDF (449KB) ( 1082 )  
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    Y zeolites are widely used in catalytic cracking, and the modification of them have attracted extensive attentions from all over the world. In this review, different methods of mesopore modification of Y zeolites in recent years are summarized, and their advantages and disadvantages are pointed out. The mesopore formation mechanisms during dealumination(steaming) and desilication(with the presence of pore-directing agents) are discussed, and the influences of dealumination and desilication on the acidity and hydrothermal stability of Y zeolites are analysed. The applications of mesopore-modified Y zeolites are also presented. At last, it concludes that the mesopore-modified Y zeolites are promising catalysts which will be used in catalytic conversion of coal, biomass and other carbonaceous materials.
    Synthesis and catalytic cracking performance of Y zeolite with sheet-like morphology
    CUI Sha, GE Jiaqi, WANG Genggeng, YANG Ying, LIU Baijun
    2018, 37(02):  576-580.  doi:10.16085/j.issn.1000-6613.2017-0935
    Abstract ( 260 )   PDF (1433KB) ( 241 )  
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    The Y zeolite with sheet-like morphology was synthesized by directing agent method, using polyethyleneglycol-600 as the morphology control agent and dispersion agent. Characterization of the molecular sieves and the catalysts was performed using SEM, XRD, N2 adsorption-desorption, Py-FTIR and NH3-TPD. Results showed that the prepared sheet-like molecular sieve had high external specific surface area. The catalytic cracking properties of the catalysts prepared with industrial octahedral and sheet-like NaY zeolites were investigated by using 1,3,5-triisopropylbenzene as the probe molecule. The experimental results showed that the catalyst with sheet-like morphology displayed higher conversion of 1,3,5-triisopropylbenzene and cracking products selectivity, compared to the industrial octahedral zeolite.
    Effects of spent SCR catalyst blending on the de-NOx activity of new catalyst
    HE Chuan, WANG Lele, YANG Xiaoning, YAO Yan, KONG Fanhai
    2018, 37(02):  581-586.  doi:10.16085/j.issn.1000-6613.2017-0873
    Abstract ( 242 )   PDF (464KB) ( 212 )  
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    A series of catalyst samples with different spent catalyst mass ratio were prepared for de-NOx activity tests and life time evaluation experiments on a home-made experiment system. The results indicated that, when the spent catalyst mass ratio was below 5%, the de-NOx efficiency was slightly lower than that of the sample without spent catalyst. However, when the spent catalyst mass ratio was increased to 10%, the de-NOx activity declined rapidly. The catalyst samples were characterized with N2 adsorption-desorption, scanning electron microscopy(SEM), X-ray fluorescence (XRF) and X-ray diffraction(XRD) analysis. The results showed that the alkali metal and As oxide from the spent catalyst could poison the samples, leading to lower de-NOx activity. In addition, the surface complexity of 15-cat was much lower than that of 0-cat, which resulted in less BET surface. The tests indicated that the de-NOx activity would be restrained under high mass ratio of spent catalyst.
    Fluidization performance and abrasive resistance of low-carbon alkane dehydrogenation catalysts
    DU Yupeng, SUN Lejing, XU Teng, FANG Deren, REN Wanzhong
    2018, 37(02):  587-591.  doi:10.16085/j.issn.1000-6613.2017-0867
    Abstract ( 264 )   PDF (421KB) ( 392 )  
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    Catalytic dehydrogenation of low-carbon alkane to high-value olefin is a high-efficient way of utilizing petrochemical resources. In this study,the fluidization performance of the catalyst PBD was investigated in terms of particle density, size distribution, and minimum fluidization velocity. The findings indicated that the catalyst PBD with appropriate particle size distribution and density belongs to Geldart A particles which can be readily fluidized. Additionally,the abrasion rate of the catalyst PBD was 0.27%, only 1/8 to 1/4 of that of catalyst R and W, which means a dramatic reduction in catalyst consumption in industrial plants.
    Research progress in preparation methods of collagen based biomaterials
    WANG Ruirui, WANG Hongru
    2018, 37(02):  592-598.  doi:10.16085/j.issn.1000-6613.2017-0969
    Abstract ( 404 )   PDF (467KB) ( 1094 )  
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    Collagen has become one of the most promising green renewable functional materials due to its strong hydrophilicity, excellent biocompatibility, weak antigenicity, and easy to be processed. In order to overcome the disadvantages of natural collagen material, such as poor thermal stability, poor water resistance, low mechanical strength, easy enzymolysis and easy pollution, the collagen is usually processed by covalent cross-linking, electrospinning, self-assembly and phase separation. Firstly, the principle of four kinds of preparation methods was introduced. The research status of the four preparation methods was described. The advantages and disadvantages of the four methods were pointed out. Then, the preparation process, structure and function difference of the four methods were compared. Finally, the prospect of collagen based biomaterials was reviewed. Results showed that as a clean and renewable material, collagen based biomaterials have broad application prospects in the fields of micro bioreactor, sensor, mart drug delivery system, and artificial light harvesting system.
    Research progress of cellulose self-assembly materials
    YAO Yijun, WANG Hongru
    2018, 37(02):  599-609.  doi:10.16085/j.issn.1000-6613.2017-0568
    Abstract ( 434 )   PDF (575KB) ( 545 )  
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    Cellulose self-assembly materials are one of the most potential natural polymer materials due to their renewability, biocompatibility, biodegradability and high mechanical properties, etc. Cellulose self-assembly materials can be constructed directly with another macromolecule polymers or via chemical modification of small molecules and the latter is the main way. In this article, the chemical modification and self-assembly of cellulose and its derivatives are introduced in detail firstly. The principles and characteristics of synthesizing assembly molecules by hydrophobic modification of long carbon chain, atom transfer radical polymerization(ATRP) of vinyl monomers, ring-opening polymerization(ROP) of aliphatic polyester monomers, and reversible addition-fragmentation chain transfer polymerization(RAFT) of amino acid monomers are analyzed, then, the latest research of cellulose self-assembly materials constructed by assembly molecules in water and non-aqueous systems are reviewed. It points out that cellulose self-assembly materials after modification possess intelligent responses and their morphologies can be controlled through the change of environment (temperature, pH, CO2, etc.). Owing to the above advantages, they have potential application values in the areas of drug carrier and controlled release, bio-sensor and bio-film materials. Finally, the outlook for advancing this area is depicted.
    Recent advances in amine-based solid sorbents for post-combustion CO2 capture
    PENG Zhaojing, ZHAO Yanjie, HUANG Chengde, DENG Shuai, ZHAO Li
    2018, 37(02):  610-620.  doi:10.16085/j.issn.1000-6613.2017-0929
    Abstract ( 377 )   PDF (614KB) ( 409 )  
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    The anthropogenic CO2 emission by combustion of fossil fuels is mainly responsible for the global warming. Post-combustion CO2 capture is one promising approach to reduce the CO2 emission from power plants. It is very important to find solid sorbents that are highly efficient, stable and cost-effective for post-combustion CO2 capture. Recently, many researchers have paid attentions to the development of novel amine-based solid sorbents because of their high CO2 adsorption capacity and selectivity and easy regeneration. Amine-based solid sorbents can be prepared by the incorporation of diverse organic amines into the pore structures of the support materials by physical impregnation, grafting or direct-synthesis. This paper reviews novel amine-based solid sorbents prepared with different supporting materials including zeolite, mesoporous silica, porous carbon materials, and metal organic frameworks(MOFs) in recent years. Finally, it is also proposed that the development of novel supporting materials with hierarchically porous structure and the selection of amines and accelerants will be hot spots in future studies.
    Research progress in surface-modification and applications of nano zinc oxide
    CHEN Xiao, SHI Qian, YANG Le, QIU Yu, SUN Qi, LEI Hua
    2018, 37(02):  621-627.  doi:10.16085/j.issn.1000-6613.2017-0508
    Abstract ( 659 )   PDF (442KB) ( 1377 )  
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    Nano zinc oxide(ZnO) is a widely used multifunctional material. The properties and applications of ZnO were introduced, and the importance of surface modification was expounded. Surface modification could cause changes in particle size, defects and surface chemical properties of ZnO. In this work, the surface modification methods were classified at first, then the influences of surface modification on the properties of ZnO were reviewed, including the optical property, antibacterial property and biotoxicity, as well as those of the ZnO/polymer nanocomposites. The relevant reasons for the influences were also analyzed from different perspectives. Appropriate surface modification can improve the stability and dispersibility of ZnO, enhance its UV resistance, photocatalysis, photoluminescence and antibacterial properties, reduce its toxicity, regulate and coordinate its properties, while improper surface modification may result in the property deterioration of ZnO. However, it is still a great challenge to comprehensively and accurately predict and achieve the advantages of surface modification. Therefore, more in-depth and systematic studies are still needed in the choice of surface modifier and surface modification methods, in the establishment of surface modification system, the surface modification mechanism and in the performance optimization.
    Research progress of MOFs-based materials in electrochemical energy storage
    CHEN Dan, YANG Rong, ZHANG Weihua, LI Runqiu, ZHU Xuyang, LU Leilei
    2018, 37(02):  628-636.  doi:10.16085/j.issn.1000-6613.2017-0926
    Abstract ( 355 )   PDF (573KB) ( 998 )  
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    Metal organic frameworks(MOFs) have attracted great attention because of their high specific surface area, adjustable pore structure and diverse composition, and the applications of MOFs have great prospects in various fields, especially for electrochemical energy storage in which great progress has made. This article summarizes the application of MOFs based materials in the field of electrochemical energy storage for lithium-sulfur batteries, lithium-ion batteries and supercapacitors in recent years. The mechanism of MOFs and their composites as host of lithium-sulfur battery cathode was introduced in detail. The physical encapsulation and chemical coordination of MOFs on active substances were discussed. In addition, it described the improved battery performance when the MOFs derived carbon material with unique pore structure, strong conductivity and rich active sites was used as the electrode material. Finally, the MOFs based materials in electrochemical energy storage is prospected and the control of heteroatoms and the design of the channels in the MOFs-based materials are thought as the focus of future research.
    Research progress of carbide-derived carbon and its application in adsorption
    WANG Hongyan, WANG Baodong, LI Junhua, ZHU Tianle
    2018, 37(02):  637-643.  doi:10.16085/j.issn.1000-6613.2017-1012
    Abstract ( 318 )   PDF (3289KB) ( 541 )  
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    Carbide-derived carbon(CDC) is a new kind of porous carbon materials with nanostructure. CDC is produced by selective extraction of metal atoms via physical (e.g., thermal decomposition) or chemical(e.g., halogenation) processes, and transforming the carbide structure into pure carbon. Its nanostructure can be controlled at atom level. This paper summarizes the synthesis and properties CDC, including its pore and structure, and applications in adsorption. It is shown that its structure such as the specific surface area, pore size and pore size distribution can be controlled accurately by the change of synthesis parameters, resulting in the structure ranges from amorphous carbon to graphite, carbon nanotubes or graphene. Understanding of the processing-structure-properties relationships facilitates tuning of the CDC to meet the requirements of certain application.
    Preparation and application of TNT molecularly imprinted microspheres
    WU Ping, CAI Shuang, GUO Jianliang, RAO Guoning
    2018, 37(02):  644-650.  doi:10.16085/j.issn.1000-6613.2017-0948
    Abstract ( 281 )   PDF (4773KB) ( 475 )  
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    The molecularly imprinted polymers(MIP) were prepared by precipitation polymerization method using 2,4,6-trinitrotoluene(TNT) as the template molecule and acrylamide(AM) as the functional monomer. The interaction between TNT and AM was studied by UV spectroscopy. It was found that TNT and AM had a strong force, which could help to form MIP with stable structure and binding ability. The morphologies of the polymers were observed by scanning electron microscopy (SEM). It was found that the polymers prepared with 100mL acetonitrile under slow stirring were better than others. The equilibrium adsorption experiments showed that there were two kinds of adsorption sites and the adsorption capacity increased with the increase of initial concentration of TNT. Kinetic adsorption experiments showed that the adsorption rate of MIP was much quicker than that of non-imprinted polymers(NIP). Meanwhile, the specific adsorption of MIP was also tested. The results showed that MIP had strong specific adsorption properties to TNT, while the adsorption to the structural analogues of TNT(DNT and RDX) was quite weak.
    Preparation and sensing properties of ZnO supporting SnO2 nanocomposites
    WEI Ying, YI Guiyun, WANG Xiaodong, XU Yawei, ZHOU Lixing
    2018, 37(02):  651-657.  doi:10.16085/j.issn.1000-6613.2017-0907
    Abstract ( 271 )   PDF (3167KB) ( 246 )  
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    SnO2/ZnO composites were synthesized by a facile hydrothermal method using SnCl4·5H2O and Zn(AC)2·2H2O as the raw material and NaOH as the precipitant, which makes SnO2 nanoparticles adhere to the surface of silkworm chrysalis-like ZnO. The structure and morphology of the obtained materials were characterized by XRD, TEM, HRTEM and BET. And the effects of temperature, ethanol concentration and other factors on the sensitivity were inverstigated. The results confirmed that the composite materials were SnO2 nanoparticles and silkworm chrysalis-like ZnO. The SnO2 nanoparticles were distributed on the surface of ZnO. The SnO2/ZnO composite exhibited good gas-sensing properties, and the sensitivity of the sensor to 200μL/L ethanol was 39.68 at the optimum operating temperature (240℃), which were almost double of that of the individual SnO2(24.53) and ZnO sensor(17.8).
    Effect of laser power and stretching force on the chemical structure and microstructure of PAN-based carbon fibers under laser graphitization
    LI Sanyang, ZHANG Youcheng, SHA Yang, YAO Liangbo, TAN Jing, LI Haoyi, CAO Weiyu, YANG Weimin
    2018, 37(02):  658-663.  doi:10.16085/j.issn.1000-6613.2017-0952
    Abstract ( 244 )   PDF (641KB) ( 337 )  
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    The graphitization of PAN based carbon fibers was carried out on a self-made laser based high temperature graphitization platform. Serials of carbon fiber samples were prepared under different laser power and different traction conditions. Then the chemical structure and microcrystal structure of the samples were studied by Raman spectroscopy and X-ray diffraction (XRD) respectively. The results showed that if the stretching force remained constant, the graphitization degree of carbon fiber increased with the laser power. When the laser power reached a certain value, the increase of graphitization degree by solely increasing the laser power became less obvious. If the laser power remained constant, as the stretching force increased, the size of graphite crystallite Lc, La increased accordingly, while d002 and the orientation angle reduced gradually. In the process of laser based graphitization of fabricating carbon fiber, exerting a certain stretching force can impel the graphite crystallite of carbon fiber to preferentially orient along the fiber axis, and finally the crystallite size is improved, and the spacing of graphite microcrystalline layer is reduced and the number of microcrystalline packing layers is increased.
    Fabrication and electromagnetic interference (EMI) shielding properties of porous functional multi-walled carbon nanotubes/epoxy composites
    CHEN Jianjun, HUANG Yuewen, LIANG Caizhen, WANG Bin
    2018, 37(02):  664-672.  doi:10.16085/j.issn.1000-6613.2017-0527
    Abstract ( 286 )   PDF (713KB) ( 556 )  
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    Free radical reaction was firstly performed to prepare maleic anhydride(MA)functionalized MWCNT(MA-MWCNT) via grafting maleic anhydride(MA) onto the side walls of multi-walled carbon nanotubes(MWCNT). MA-MWCNT, epoxy, waterborne curing agents prepared from ricinoleic acid(RA) and tetraethylenepentamine(TEPA), glaze powder and water were then used to fabricate porous functional multi-wall carbon nanotube/epoxy composites through epoxy-water-filler suspended emulsion polymerization. Finally, Raman spectra, XRD, FTIR and XPS were used to characterize the functional multi-wall carbon nanotube. The morphologies of the composites, the electrical conductivity and electromagnetic interference(EMI) effectiveness were measured by scanning electron microscopy (SEM), surface resistance measuring instrument and vector network analyzer, respectively. The results revealed that the dispersing performance of MWCNT and EMI effectiveness of the MWCNT/epoxy composites were improved after the functionalization of MWCNT with maleic anhydride. The electrical conductivity and electromagnetic interference(EMI) effectiveness of the composites increased as the increase of MWCNT content. Higher EMI effectiveness value will be obtained when functional MWCNT were added compared with the pristine MWCNT. Besides, the porous composites also have better EMI properties than the solid composites. When the content of functional MWCNT was 3%, the porous composites have the best EMI properties and the highest EMI effectiveness could reach 31.1dB.
    Preparation and properties of superhydrophobic PVDF microporous composite membrane
    WANG Zhiying, HAN Chengzhi, YU Yongbo, DENG Huining, LI Chunli
    2018, 37(02):  673-680.  doi:10.16085/j.issn.1000-6613.2017-0777
    Abstract ( 292 )   PDF (4384KB) ( 326 )  
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    A novel method is reported to fabricate superhydrophobic polyvinylidene fluoride(PVDF) microporous composite membrane. PVDF microporous membrane prepared by phase inversion was used as the support membrane. Functional multi-walled carbon nanotubes (MWCNTs) were deposited on the support membrane by constant pressure filtration, then the prepared membrane was coated with polydimethylsiloxane(PDMS). The obtained composite membrane exhibited super-hydrophobic property with the water contact angle of 162° and the sliding angle of about 10°. The morphology, contact angle, N2 flux and the tensile strength of the membranes were tested. The effect of the concentration of MWCNTs and PDMS in the coating solution on the structure and properties of the membranes were also investigated. The results showed that the addition of MWCNTs strengthened the nanostructures of the membrane surface and improved the roughness of the membrane simultaneously. The PDMS coating reduced the surface energy of the membrane. Their synergistic effect increased the contact angle and decreased sliding angle of the composite membranes significantly. Compared with the hydrophobic PVDF support membrane, the hydrophobicity of the composite membrane was better, and the elongation at breaking was doubled. In the vacuum membrane distillation of the simulated seawater, the operational stability and antifouling property of the composite PVDF membrane prepared in this study were greater than those of the hydrophobic PVDF support membrane. And the merits of high permeation flux and rejection coefficient were maintained.
    Numerical simulation of solidification characteristics of graphene nanofluid as phase change material
    CHEN Chen, PENG Hao
    2018, 37(02):  681-688.  doi:10.16085/j.issn.1000-6613.2017-0954
    Abstract ( 273 )   PDF (2254KB) ( 556 )  
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    Graphene nanofluid is a promising phase change material for improving the efficiency of cool storage. The solidification characteristics of water based graphene nanofluid were numerically investigated; enthalpy-porosity method was adopted to track the solid-liquid interface; the effects of graphene nanosheet mass fraction, cool storage cavity size and geometry on the solidification time and solid-liquid interface evolution were analyzed. The results showed that the solidification time decreased significantly with the increase of graphene nanosheet mass fraction. In a circular cool storage cavity with a diameter of 72mm, the solidification time for 1.2% graphene nanofluid was 30.1% less than that for the deionized water, which was consistent with the experimental results. With the decrease of circular cavity diameter, the solidification time for graphene nanofluid significantly decreased, but the enhancement effect of thgraphene nanosheet on the solidification was weakened. For the same sectional area, the moving velocity of solid-liquid interface during the solidification in a triangular cavity is larger than that in the circular and square cavities, which indicated that the triangular cavity was more conducive to the promotion of solidification process. For those three types of cavities, the solidification occurred at the bottom of cavity in the initial stage; the solid-liquid interface was similar to the shape of the cavity itself and tended to be circular in the middle and later stages, respectively.
    Preparation and cyclic properties of low temperature phase change materials of n-caprylic acid and myristic acid
    LI Yuyang, ZHANG Xuelai, XU Xiaofeng, MUNYALO Jotham Muthoka, CHEN Yue, CHEN Qiyang
    2018, 37(02):  689-693.  doi:10.16085/j.issn.1000-6613.2017-0802
    Abstract ( 282 )   PDF (459KB) ( 460 )  
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    This paper developed a binary organic composite phase change material that is used for pharmaceutical refrigerating transportation system with the phase change temperature of 2-8℃. The material was mixed with a mixture of n-caprylic acid and myristic acid. First two binary eutectic points were determined through the theoretical calculation method to calculate the eutectic mixture ratio, phase transition temperature and latent heat value. Then six different proportion of mixtures around the eutectic point were made. The low melting point temperature of n-caprylic acid and myristic acid was found to be 6.2℃, the sub-cooled temperature by 0.5℃. The mass ratio was found to be 87:13. The phase transition temperature of the composite phase change materials was 7.13℃ and the latent heat of phase change measured by differential scanning calorimeter (DSC)was found to be 146.1J/g. The thermal conductivity of eutectic liquid was measured by Hot Disk and was found to be 0.232 W/(m·K). It was found that the phase transition temperature and latent heat value of the composite phase change materials of n-caprylic acid and myristic acid were 40 times and 80 times more respectively. However, it was found that the phase change temperature and latent heat value were not altered. The results showed that the composite had great potential in the cold storage system, especially in medicine cold storage transportation system.
    Synthesis of salidroside by β-glucosidase nanogel in non-aqueous media
    WEI Shenghua, QIAN Wei, ZHOU Qinghua, XU Hang, GUO Lianghao, XU Shuchun, WANG Hanjie
    2018, 37(02):  694-701.  doi:10.16085/j.issn.1000-6613.2017-0814
    Abstract ( 300 )   PDF (1309KB) ( 332 )  
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    To efficiently prepare salidroside, the encapsulation of β-glucosidase into nanogel was accomplished via the two-step in situ polymerization and used as the catalyst to synthesize salidroside with glucose and tyrosol as substrates in a non-aqueous system by reverse hydrolysis. The tolerance of the enzyme nanogel and the effects of different organic solvents, water content, enzyme dosage, pH, temperature and the substrate concentration on the synthesis of salidroside were investigated. Because the enzyme nanogel could effectively enhance the thermo-stability and the tolerance of organic solvents, β-glucosidase nanogel was well suitable for the synthesis of salidroside by reverse hydrolysis. The results showed that t-butanol was the best organic solvent whenthe water content of system was 5%, the enzyme dosage was 4.0U/mL, the pH was 6.0, the reaction temperature was 60℃, and the concentrations of glucose and tyrosol were 300mmol/L and 900mmol/L, respectively. Under the optimized conditions, the concentration of salidroside was 71.13mmol/L, and the yield could reach up to 23.7% after reaction for 96h. The research provided a new and more effective approach for enzymatic synthesis.
    Inhibition of Ponatinib on wild-type and T315I mutant BCR-ABL1 kinase based on molecular simulation
    CHEN Qing, WANG Jianyi
    2018, 37(02):  702-707.  doi:10.16085/j.issn.1000-6613.2017-0891
    Abstract ( 218 )   PDF (863KB) ( 355 )  
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    The drug Ponatinib had a strong inhibitory effect on wild-type and T315I mutant BCR-ABL1 kinase, but its inhibition mechanism was still unknown. To have a better understanding of the interaction mechanism between Ponatinib and BCR-ABL1 kinase, the effect of Ponatinib on the conformational changes of BCR-ABL1 kinase was studied by molecular dynamics simulation at first, and then the binding free energy of complex was calculated by the MM-PBSA method. The results indicated that the P-loop and hinge region of wild-type BCR-ABL1 kinase approached each other induced by Ponatinib, leading to the closure of the binding pocket of wild-type BCR-ABL1 kinase, which would be favorable to the binding of drug. In contrast, the P-loop and hinge region of T315I mutant BCR-ABL1 kinase move far away from each other induced by Ponatinib, resulting in the opening of the binding pocket of T315I mutant BCR-ABL1 kinase, which was no advantage for kinase binding with drug. The binding free energy of Ponatinib bound to wild-type and T315I mutant BCR-ABL1 kinase were -58.57kcal/mol and -43.54kcal/mol, respectively. The results showed that the inhibitory ability of Ponatinib on wild-type BCR-ABL1 kinase was significantly stronger than that of T315I mutant, which was consistent with the experimental inhibition activity reported in the literature. This study provided important understanding of the molecular mechanism of target proteins and inhibitors and the design of a new drug.
    Preparation of copolymers containing nitroxyl radical and sulfonic acid and their catalytic performances
    DU Huili, CUI Xiaofei, LIU Shaojie
    2018, 37(02):  708-713.  doi:10.16085/j.issn.1000-6613.2017-0886
    Abstract ( 239 )   PDF (374KB) ( 412 )  
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    With 2,2'-azobis(2-methylpropionitrile) as the initiator, and sodium p-styrene sulfonate (SSS) and 2,2,6,6-tetramethylpiperidine-4-yl-1-oxyl (TMPM) as the monomers, the copolymer of P(TMPM-co-SSS) was synthesized via free radical copolymerization. Followed by oxidizing it with the mchloroperbenzoic acid, the nitroxyl copolymer of P(TMA-co-SSS) was obtained. Finally acidified by the hydrochloric acid, the bifunctional copolymer of P(TMA-co-HSS) was obtained. Selective catalytic oxidation performances of P(TMA-co-HSS) for benzyl alcohol in a biphasic water-oil NaClO oxidation system were studied. The results showed that the catalytic activity of P(TMA-co-HSS) was good and the yield was up to 89%. Furthermore, the copolymers had excellent recyclability and the activity was not decreased significantly after 3 cycles. The catalytic performance of P (TMA-co-HSS) as a solid acid catalyst for the synthesis of ethyl N-phenylformimidate was also studied. Its catalytic performance was compared with p-toluene sulfonic acid and PHSS. The results showed that the catalytic activity of P(TMA-co-HSS) was excellent and the yield was up to 97%, comparable to p-toluene sulfonic acid. Furthermore, P(TMA-co-HSS) had excellent recyclability and the activity was not decreased significantly after 5 cycles.
    Present status and prospect of red mud resource utilization and safety treatment
    LI Bin, ZHANG Baohua, NING Ping, HE Liwei, ZUO Xiaolin
    2018, 37(02):  714-723.  doi:10.16085/j.issn.1000-6613.2017-0843
    Abstract ( 636 )   PDF (464KB) ( 1392 )  
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    This paper reviews the advances in the mechanism research of function and application about the red mud in recent years in the following aspects:valuable components recovery, wastewater treatment, gas purification, catalyst research, and the improvement of building materials and soil, through the analysis of physical and chemical characteristics of red mud. The advantages and application prospects of each application direction were explained. It was pointed out that the red mud contains a large number of alkaline substances and heavy metals, which are the most important factors to restrict the resource utilization and cause potential safety problems. Therefore, the alkali removal technology of red mud and the research of the red mud on the toxic leaching were emphasized. The utilization methods of red mud resources are scattered at home and abroad, while the systematic research on red mud utilization is insufficient, and the red mud hasn't achieved fully utilization, neither does the realistic and potential environmental problems it has generated been solved. Based on the purpose of about red mud disposal "reduction, harmless and recycling" principle and the situation of our country, we put forward some technical measures for comprehensive treatment and utilization of red mud about"gas purificationresource recovery-preparation of building materials ", which offers a lot of new research and industrialized ideas for resource utilization of large-scale industrial solid waste-red mud.
    Advances in cadmium removal from wastewater by silica-based materials
    HE Yuxuan, ZHANG Liming, GUO Feifei, LI Penggang, PENG Wen, LIU Hang, LOU Yongming
    2018, 37(02):  724-736.  doi:10.16085/j.issn.1000-6613.2017-0949
    Abstract ( 265 )   PDF (894KB) ( 1267 )  
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    In recent years, silicon-based materials, which has high specific surface area, multi-mesopore channels and good thermal stability, have been widespread concerned, and used as adsorbents for environmental problems. This study is a review of the recent literatures on the use of modified silicon-based materials for Cd adsorption. The maximum adsorption capacity and adsorption mechanism of the cadmium ions in the solution were analyzed by comparing the modified silicon materials of organic materials, inorganic materials and polymers. The adsorption process and capacity of various adsorbents was compared by adsorption isotherm and dynamical model. The analysis shows that the increase of hydrophilicity and functional groups on the surface of the material is capable of removing cadmium ions from water. It is pointed out that the preparation of high selectivity, high adsorption capacity and improving recyclability will be the research focus of silicon-based material modification. In addition, industrial and agricultural waste materials being highly efficient, low cost and renewable source of biomass can be exploited for Cd remediation. Furthermore, these materials can be used to prepare new silicon materials for better efficiency and multiple reuses to enhance their applicability.
    Research progress on Fe(Ⅱ)EDTA regeneration accompanied wet denitrification
    HE Feiqiang, DENG Xianhe, CHEN Min
    2018, 37(02):  737-743.  doi:10.16085/j.issn.1000-6613.2017-0898
    Abstract ( 344 )   PDF (540KB) ( 735 )  
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    In recent years, with the increasingly serious situation of air pollution, the research of control technology of NOx emission in coal-fired flue gas is particularly critical. Wet denitrification with Fe(Ⅱ)EDTA has been widely researched due to the fast absorption rate, large complex capacity and good capacity of wet desulfurization, but Fe(Ⅱ)EDTA can be easily oxidized by oxygen to Fe(Ⅲ)EDTA, losing the complexing ability to NO. Therefore, in order to improve the denitrification efficiency of Fe(Ⅱ)EDTA, it is necessary for Fe(Ⅱ)EDTA regeneration. In this paper, the research progress of the regeneration technology Fe(Ⅱ)EDTA was presented. The principles and properties of the regeneration with sulfur compounds, metal powder, urea, organic compound, catalyst, and microorganism were respectively explained. Then their own advantages and shortcomings were elaborated and the industrialization with these regeneration technologies were analysed. Finally, it is pointed out that microbial regeneration of Fe(Ⅱ)EDTA is a promising regeneration technique. Studying Fe(Ⅱ)EDTA regeneration with aerobic bacteria, exploring the equipment of microbial Fe(Ⅱ)EDTA regeneration, and developing an efficient absorption process integrated microbial regeneration of Fe(Ⅱ)EDTA, is the future direction of Fe(Ⅱ)EDTA regeneration.
    Adsorption treatment of phenolic wastewater by activated carbon: a review
    FANG Mengxiang, YAO Peng, CEN Jianmeng, YU Chunjiang, WANG Qinhui, LUO Zhongyang
    2018, 37(02):  744-751.  doi:10.16085/j.issn.1000-6613.2017-1015
    Abstract ( 387 )   PDF (427KB) ( 829 )  
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    Phenolic wastewater is a common chemical wastewater which has a great harm to the environment and biological. As a good adsorbent, activated carbon is widely used in sewage treatment, especially in adsorption treatment of phenolic wastewater. The latest researches focus on the development and utilization of various carbonaceous materials, and explore the methods of preparation and modification to improve the phenolic adsorption properties of activated carbon. Some mechanism studies pay attention to the pore structure and surface functional groups of activated carbon, as well as the effect on the properties of phenolic adsorption. In this paper, the preparation and modification of activated carbon were introduced, the characteristics and mechanism of phenolic adsorption by activated carbon were summarized, the main influencing factors of the adsorption process were analyzed, the research directions and prospects were deduced. The analysis shows that raw materials with high carbon content are suitable for the preparation of activated carbon, especially carbonaceous waste. The adsorption capacity of phenol in activated carbon is affected by the specific surface area and surface functional groups, which is significant for the preparation and modification of activated carbon. It is important to control the particle size, pH, temperature, adsorption time, competitive adsorption and other factors when activated carbon is used to phenol adsorption in the specific application.
    Research status and research ideas of chrome tanning waste disposal
    JIANG Xuguang, FANG Chunqi, JIN Yuqi, LÜ Guojun, YUAN Weizhong, CHEN Xijiong, LUO Weizhong
    2018, 37(02):  752-760.  doi:10.16085/j.issn.1000-6613.2017-0860
    Abstract ( 328 )   PDF (1478KB) ( 788 )  
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    The disposal of chromium containing tannery waste can recover the energy, chromium and collagen, but the unreasonable disposal has caused environment pollution and waste of resources. In this paper, the source and the current situation of disposal of chromium containing leather wastes were described. Based on the latest domestic and foreign chromium tanning waste processing literatures, the related researches of chrome tanning waste treatment and disposal were summarized. The disposal methods can be divided into two categories:direct treatment and indirect treatment. Three direct treatments including adsorbent, pyrolysis, incineration and four indirect treatments including oxidation, acid hydrolysis, alkaline hydrolysis, enzymatic hydrolysis were described in detail. The principle, advantages and disadvantages,and application prospect of each disposal method were analyzed. The main functions of various disposal methods were briefly described. Besides, the advantages and disadvantages of each method were compared. At last, the research ideas of chromium leather waste disposal were put forward. Especially, the mechanism of combustion and pollutant emission during the process of pyrolysis and incineration of chromium containing tannery wastes will be studied.
    Effects of mixing on magnesium hydroxide coagulation performance and floc properties
    XIAO Shumin, ZHAO Jianhai, WEI Lei, CHI Yongzhi
    2018, 37(02):  761-766.  doi:10.16085/j.issn.1000-6613.2017-0961
    Abstract ( 254 )   PDF (5561KB) ( 365 )  
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    The effect of mixing conditions on the coagulation performance and floc properties of magnesium hydroxide was studied by the reaction of magnesium chloride in an alkaline condition and treatment of simulated reactive orange dyes wastewater. Based on the flocculation index(FI) and the zeta potential, the mechanism of floc formation was discussed, and the floc morphology was observed to reveal the relationship between floc formation process and coagulation performance. The results showed that the rapid mixing time is favorable for floc formation, and the optimum time is 45s. While longer rapid mixing time will result in floc broken and poor treatment effect. Similarly, the best slow mixing time is 3min. Prolong mixing time will lead to floc broken. Using the optimum mixing time, it was found that the mixing speed was also the main factor affecting the coagulation performance and floc properties. Lowering rapid and slow mixing speeds are not conducive to the formation and growth, respectively. However, higher mixing speed will make the floc broken and consequently reduce the treatment efficiency. When dosage of Mg2+ is 150mg/L under laboratory conditions, the optimum conditions for the coagulation performance of magnesium hydroxide were as follows:rapid mixing for 45s at 250r/min or G value of 126.3, followed by slow mixing for 3min at 60r/min or G value of 18.5. Coagulation mechanisms of adsorption, charge neutralization and precipitate enmeshment should be suitable for this process. The removal efficiency of reactive orange dye water is more than 95%.
    Preparation of magnetic Fe3O4@C composites under ambient pressure and their adsorption of methylene blue
    CHEN Qiliang, WANG Saidan, ZHANG Jia, LI Tao, REN Baozeng
    2018, 37(02):  767-774.  doi:10.16085/j.issn.1000-6613.2017-0868
    Abstract ( 289 )   PDF (3706KB) ( 628 )  
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    Under ambient temperature and pressure, the magnetic Fe3O4@C was synthesized by sulfuric acid sucrose carbonization method and with Fe3O4 synthesized by co-precipitation and as the carrier. The resulting products were characterized by Fourier transform infrared spectra(FTIR), X-ray powder diffraction(XRD), scanning electron microscope(SEM), transmission electron microscope (TEM), and magnetic property measurement system(MPMS). The Fe3O4@C was tested for the ability to remove methylene blue(MB). The effects of adsorbent dosage, solution pH, adsorption temperature and oscillating time on the adsorption process were investigated. The results showed that there are a lot of irregular holes in the surface of Fe3O4@C and its saturation magnetization is 18.45emu/g. When the initial concentration of MB is 100mg/L, adsorbent dosage is 1g/L, adsorption time is 150min, adsorption temperature at 25℃, pH=12, the maximum adsorption capacity reaches 96.74mg/g. The experimental data fitted well with Langmuir model. The adsorption kinetic fitted well with the pseudo-second-order kinetic, and the adsorption of MB was an endothermic and the confusion degree increase process. Fe3O4@C could be regenerated by washing with H2SO4 aqueous solution.
    Adsorption of divalent mercury by copper/iron modified activated carbon
    HU Yanan, WANG Xueqian, NING Ping, CHENG Jinhuan, TAO Lei
    2018, 37(02):  775-782.  doi:10.16085/j.issn.1000-6613.2017-0984
    Abstract ( 224 )   PDF (2113KB) ( 441 )  
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    With the development of industry, divalent mercury pollution as one of the environmental issues has been paid more and more attention around the world. In this paper, copper and iron-based[CuCl2, FeCl3, Cu(NO3)2] modified activated carbon were prepared by over-volume impregnation method. The effects of modified activated carbon prepared at different concentrations and calcination temperature on the removal of divalent mercury(HgCl2) in simulated flue gas were investigated. Through the comparative experiments, both copper-based and iron-based activated carbon have a good adsorption effect on mercury-containing flue gas. The 0.01mol/L of copper chloride modified activated carbon calcined at 300℃ is the best removal of mercury chloride flue gas modified activated carbon, the adsorption capacity reached 4.55mg/g. On this basis, the physical and chemical characteristics were studied by using XRD, BET, SEM/EDS and XPS. It was proved that the adsorption of copper chloride and iron-based activated carbon is the result of the interaction between physical adsorption and chemical adsorption, and the corresponding explanation was given to provide some ideas for the follow-up scientific research.
    Effects of different carbon sources on biological denitrification of wastewater at low temperature with adding redox mediator
    YUAN Hongying, SUN Yeyi, LI Yuanling, SUN Jinxiu, WANG Xiaopei
    2018, 37(02):  783-788.  doi:10.16085/j.issn.1000-6613.2017-1016
    Abstract ( 300 )   PDF (522KB) ( 410 )  
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    The effect of denitrification of low temperature sewage is poor. It is found that the redox mediator in low temperature is beneficial to denitrification process. Different carbon sources have different effects on denitrifying nitrogen removal. The effect of different carbon sources(sodium propionate, methanol, ethanol and sodium acetate) on the biological denitrification of wastewater at low temperature with adding redox mediator 1,2-naphthoquine-4-sulfonic acid(NQS)were investigated. The effects of concentration of nitrate, total nitrogen and nitrite, removal efficiency and denitrification rate, chemical oxygen demand(COD) and redox potential (ORP) on the different carbon sources were characterized. The results showed that the highest denitrification rate was obtained when sodium propionate was used as carbon source, up to 7mgNOx--N/(gVSS·h), and it is 8 times, 2.6 times and 3.6 times of methanol[0.88 mgNOx--N/(gVSS·h)], ethanol[2.72mgNOx--N/(gVSS·h)] and sodium acetate[1.97mgNOx--N/(gVSS·h)] as carbon source, respectively. The maximum removal efficiency of nitrate was 61.5%, which was about 6.9 times, 9.3 times and 4 times higher than that of methanol(8.9%), ethanol(6.6%) and sodium acetate(15.3%) as carbon source. The maximum removal efficiency of total nitrogen was 47.4%, which was about 5.2 times, 4.6 times and 4.6 times that of methanol (9.1%), ethanol(10.3%) and sodium acetate(10.3%) as carbon source.
    CO2 absorption kinetic study based on non-aqueous mixed solvent system of amino acid ionic liquids with polyethylene glycol as solvent
    LI Jun, HE Wenjun, ZONG Hongyuan, QI Zhiwen, YANG Weimin
    2018, 37(02):  789-795.  doi:10.16085/j.issn.1000-6613.2017-0862
    Abstract ( 236 )   PDF (645KB) ( 312 )  
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    The non-aqueous mixed solvent system based on amino acid ionic liquids(AAILs) and polyethylene glycol 400(PEG400) shows many advantages, such as extremely low vapor pressure, good thermal stability, low viscosity and regeneration energy, high CO2 capacity and selectivity, which is suitable for the pre-combustion process facing high absorption temperature and pressure conditions. The CO2 absorption rates for three kinds of AAILs with tetrabutylphosphonium ([P4444]+) as cation, glycine(Gly), alanine(Ala), proline(Pro) as anions in PEG400 were determined by pressure drop method, and then the relevant absorption kinetic model was developed. The absorption rate were ranked as[P4444] [Gly]-PEG400 > [P4444] [Pro]-PEG400 > [P4444] [Ala]-PEG400 at 333.15K and[P4444] [Pro]-PEG400 > [P4444] [Gly]-PEG400 > [P4444] [Ala]-PEG400 at 373.15K. According to the absorption kinetic results, the CO2 absorption by AAIL-PEG400 system was fast reaction. Based on the absorption model, the key kinetic parameters were obtained, providing the basic data and principle of design for the coming industrial development and process design.
    Water quality characteristics and economic analysis of marine water generating machine
    SU Chuangjian, TIAN Zhongxuan, XIONG Yun, MA Jianan, HUANG Zhenfei, ZHANG Fengming
    2018, 37(02):  796-802.  doi:10.16085/j.issn.1000-6613.2017-0995
    Abstract ( 317 )   PDF (1026KB) ( 480 )  
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    Seawater desalination device is one of the necessities on ocean going vessels. It has a great significance to analyze the characteristics of freshwater and the seawater desalination economy. A performance testing platform for plate-type desalination system was built to study the influence of vacuum degree on pH and the electrical conductivity of freshwater, as well as the effect of feed concentration and vacuum degree caused on total dissolved solids(TDS). Meanwhile, this paper established freshwater cost mathematical model to investigate the influence of water production caused by vacuum degree and feed flow on the cost of seawater desalination. Then the sensitivities of oil price, fresh water price and sailing distance of fishing vessel to the cost of fresh water was analyzed further. The results showed that, in the case of constant vacuum degree, the TDS value of freshwater increased with the increase of the feed salinity. Moreover, the vacuum degree had minor effect on pH but strong influence on electrical conductivity. TDS and cost decreased as the vacuum degree increase. Furthermore, when the feed flow was 150L/h, water production was optimal and the cost of freshwater was the lowest. Lastly, the cost difference of seawater desalination was most sensitive to oil price and the cost of freshwater production was always lower than the fresh water transportation fee.
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