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Table of Content
05 January 2016, Volume 67 Issue 1
    CIESC Journal(HUAGONG XUEBAO)Vol.67 No.1 Janurary 2016
    2016, 67(1):  0-0. 
    Abstract ( 57 )   PDF (20135KB) ( 104 )  
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    Origin of common problems in fast coal pyrolysis technologies for tar: the countercurrent flow of heat and volatiles
    LIU Zhenyu
    2016, 67(1):  1-5.  doi:10.11949/j.issn.0438-1157.20151718
    Abstract ( 311 )   PDF (481KB) ( 588 )  
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    This paper analyzes fast coal pyrolysis technologies from a chemical reaction engineering point of view. It shows that the volatiles generated from coal transport in a direction against that of the heat transfer, and that the principle behind the fast coal pyrolysis technologies, i.e. reducing pyrolysis time by increasing the heating source temperature, may not reduce the reactions of volatiles as expected. Rather it promotes the reactions of volatiles leading to a low tar yield and formation of coke fines. Compared with the reduction in reaction time of volatiles the reduction in pyrolysis temperature is more important for reducing the volatiles' reaction (cracking), and therefore is favorable for a high tar yield and less coke formation in tar.

    Perspective on catalyst investigation for CO2 conversion and related issues
    LIU Changjun, GUO Qiuting, YE Jingyun, SUN Kaihang, FAN Zhigang, GE Qingfeng
    2016, 67(1):  6-13.  doi:10.11949/j.issn.0438-1157.20151488
    Abstract ( 339 )   PDF (1297KB) ( 2110 )  
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    CO2 utilization has received worldwide attention. Effective utilization of CO2 becomes an urgent challenge. As such, developing catalysts and catalytic processes for effective CO2 conversion will contribute positively to reducing net CO2 emission. Recent developments of catalysts for CO2 hydrogenation to methanol, CO2 methanation and CO2 reforming of methane have been briefly reviewed. In particular, novel catalysts developed through computational catalysis and intensified catalyst preparation were presented. The importance of CO2 anion in CO2 reduction has been discussed. The plasma enhanced catalyst preparation was used as an example to demonstrate the importance of the multi-disciplinary efforts. Catalysts with optimized structures for heat transfer performance and distribution of active sites for CO2 conversion have also been discussed. Because of the complexity of global warming, some issues (for example the influence of change in the terrestrial magnetic field induced by human activity) are still not clear and call for more fundamental studies.

    Discrete simulation based on EMMS paradigm and its applications in chemical engineering
    XU Ji, LU Liqiang, GE Wei, LI Jinghai
    2016, 67(1):  14-26.  doi:10.11949/j.issn.0438-1157.20151468
    Abstract ( 126 )   PDF (17883KB) ( 125 )  
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    Chemical engineering systems typically involve three levels of chemistry, chemical engineering and process system engineering. Each level consists of micro-, meso-and macro-scales, such as the particle, particle cluster and reactor scales in the chemical engineering level. The evolution of the micro-scale elements is naturally described by discrete simulation. However, due to the large number of elements existing in these systems, engineering simulations are mostly based on continuum methods which describe their statistically averaged behaviors and overlook the effects of meso-scale structures, leading to low accuracy and predictivity. This review will explain how this problem can be tackled in a systematic approach that keeps the structural consistency of the problem, physical model, software and hardware, and will demonstrate how discrete simulations with high accuracy, capability and efficiency can be carried out for engineering systems, such as complex molecules, granular flow, and gas-solid fluidization. Realization of virtual process engineering (VPE) is prospected finally.

    Homoporous membranes
    WANG Yong, XING Weihong, XU Nanping
    2016, 67(1):  27-40.  doi:10.11949/j.issn.0438-1157.20151113
    Abstract ( 224 )   PDF (13096KB) ( 954 )  
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    Homoporous membranes (HOMEs) are featured as ordered through pores with homogenous pore sizes and pore geometries. HOMEs are the key to improve the separation precision, and to simultaneously increase selectivity and permeability. The concept of HOMEs and their structural characteristics are discussed at first. HOMEs are not only just a type of membranes with new structures but also represent one important aspect in the development of membrane separation. Then, the diverse methods to prepare HOMEs are summarized, and their specific advantages and disadvantages are discussed. Homoporous structures with tunable pore sizes typically in the range of 10—50 nm can be achieved based on the microphase separation of block copolymers (BCPs). The BCPs-enabled methods are distinguished from others for their simple processing, low cost, no need of cumbersome devices, and upscalability. The mechanism of selective swelling-induced pore generation of amphiphilic BCPs, its uniqueness in the tuneability of pore sizes and the geometries (including cylindrical and slitted-shaped pores), and inherently permanent hydrophilicity are discussed in detail. The perspectives of HOMEs derived from BCPs are finally discussed and the bottleneck in the BCP raw materials is identified. Furthermore, focused studies on HOMEs with pore sizes <10 nm, the design of new pore geometries with enhanced permselectivity and the expanded applications of HOMEs in diverse fields are suggested.

    Green process system engineering
    ZHANG Suojiang, ZHANG Xiangping, NIE Yi, BAO Di, DONG Haifeng, LÜ Xingmei
    2016, 67(1):  41-53.  doi:10.11949/j.issn.0438-1157.20150611
    Abstract ( 242 )   PDF (2817KB) ( 428 )  
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    One of the main tendencies of sustainable chemical engineering is to develop green technologies with the aim of eliminating pollution by preventing it in the first place, and thus, any breakthrough of single unit technology could make significant contributions to a new green technology. However, process engineering is a complex system which covers multiple units and sub-systems, including utilities, waste treatment and so on. Hence, besides single technology innovation, the whole chain covering raw material substitute, unit intensification and system should be highlighted during process development, and meanwhile considering the economic and environmental constraints. Also, along this chain, the novel materials/solvents and processes innovation are important for the process greening. On the base of the principles of system engineering and considering the research frontiers of the green process engineering, and taking new ionic liquids as key material, this article reviews the latest progresses in the aspects of raw material substitution, solvent innovation, transfer properties and process integration. The proposed viewpoints and methodology could become important bases to develop new green technologies, and also construct the science of green process system engineering subject.

    Recent progresses in water oxidation over layered double hydroxide catalysts
    WANG Ruirui, ZHAO Youjing, SHAO Mingfei, XIANG Xu, DUAN Xue
    2016, 67(1):  54-72.  doi:10.11949/j.issn.0438-1157.20151766
    Abstract ( 281 )   PDF (31285KB) ( 400 )  
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    Obtaining fuels (e.g. hydrogen) from solar water splitting is one of the important pathways to develop clean energy. The water oxidation of half-reaction of water splitting is an important and speed-limited step in overall water splitting. To develop efficient, stable, and easy-made water oxidation catalysts (WOCs) is the key to achieve sufficient water splitting. Layered double hydroxides (LDHs) have received extensive attention in catalytic water oxidation because of its adjustable chemical compositions and unique two-dimensional layered structure. Besides acting as electrochemical water oxidation catalysts, LDHs also exhibit advantages in photo-(photoelectro-)chemical water oxidation. The progress in the LDHs and their composites as WOCs is summarized. It is expected that this review could provide inspiring ideas and helpful guidelines in the structural design of high-efficiency water oxidation catalysts.

    Stabilization mechanism of supported metal catalyst
    YANG Xiaoli, SU Xiong, YANG Xiaofeng, HUANG Yanqiang, WANG Aiqin, ZHANG Tao
    2016, 67(1):  73-82.  doi:10.11949/j.issn.0438-1157.20151556
    Abstract ( 91 )   PDF (2779KB) ( 438 )  
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    Supported metal catalysts play a pivotal role for many reactions in industrial processes, including petroleum refining, environmental protection and materials synthesis. However, the active metal centers suffer from severe sintering under real working condition, which will subsequently lead to a loss of its activity. Therefore, the stability of supported catalysts becomes a critical issue to its catalytic application. In this review, the aggregation and stabilization mechanisms of supported metal catalyst were briefly discussed according to the two different aggregation models of metal particles, i.e., Ostwald ripening and coalescence of smaller particles. Accordingly, the corresponding stabilization strategies, including physical methods based on encapsulation and chemical methods by forming chemical bonds, were introduced. The understanding of stabilization mechanism of supported metal catalyst would not only benefit for the development of new catalysts with promoted stability, but also provide theoretical guidance for the optimization of industrial catalysts.

    Environmental behavior of siloxane in wastewater treatment plants
    WANG Yi, CHEN Chuan, ZHANG Zifeng, REN Nanqi
    2016, 67(1):  83-88.  doi:10.11949/j.issn.0438-1157.20151433
    Abstract ( 154 )   PDF (399KB) ( 366 )  
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    Silicon atom and oxygen atom are arranged alternately in the formation of the main chain skeleton of siloxane. Due to the characteristics of high hydrophobicity, lubricity and stability, siloxane is widely employed as a raw material in lubricants, sealants, cosmetics and personal care products etc., and it is also applied in producing textile goods and superficial coating materials frequently. It is the environmental characteristics of high persistence, biological enrichment and reproductive toxicity that have drawn increasing attention to volatile methyl siloxane (VMS) during the past few years. This study outlines the context of the utilization and distribution of VMS, and its environmental behavior and fate in water treatment plants(WWTPs) are also discussed both at home and abroad. The current removal method of VMS adopted by WWTPs is primarily via absorption which contributes to over 90% of the reduction of that in influent. The majority of the rest is further eliminated by atmospheric volatilization and biodegradation. However, the mechanism of the biodegradation of VMS in water environment currently remains unclear, and it is suggested that the further study should place more attention to the analysis of the principle of the transformation and the mechanism of biodegradation of VMS in sludge.

    Gas adsorption and separation in metal-organic framework: application of classical density functional theory
    LIU Yu, ZHAO Shuangliang, HU Jun, LIU Honglai
    2016, 67(1):  89-96.  doi:10.11949/j.issn.0438-1157.20151403
    Abstract ( 155 )   PDF (7015KB) ( 803 )  
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    This article reviews the recent progress on predicting the adsorption properties of metal-organic framework by using classical density functional theory and focused on the application of the classical density functional theory to the high-throughput screening, which is accelerated by Fast Fourier Transform. Comparing to the conventional molecular simulations, the advantage of the accelerated classical density functional theory is the calculation speed, especially for simple small molecule systems, which makes the high-throughput screening on MOF materials feasible. However, it appears that there is a lack of efficient method to deal with the complicated molecules. How to construct a reasonable free energy functional of complicated fluid is the main challenge to state of art classical density functional theory.

    Review of enhanced boiling heat transfer over micro-pin-finned surfaces
    WEI Jinjia, ZHANG Yonghai
    2016, 67(1):  97-108.  doi:10.11949/j.issn.0438-1157.20151107
    Abstract ( 128 )   PDF (5057KB) ( 458 )  
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    Boiling heat transfer has significant application under normal gravity and under microgravity in space due to its high efficiency in heat transfer with phase change. Using treated surfaces is an alternative passive technique for enhancing boiling heat transfer. Forced convection and jet impingement, which are considered as the most promising cooling method, are active techniques. Combination of these passive and active techniques is an effective way to improve the heat transfer capability. The results of enhanced boiling heat transfer over our self-developed micro-pin-finned surfaces are reviewed in this paper, including pool boiling, flow boiling, jet impingement, flow-jet combined boiling heat transfer under normal gravity, and pool boiling heat transfer under microgravity. The results of enhanced boiling heat transfer over micro-pin-finned surfaces with different heat transfer modes are compared with those over other structured surfaces, and the advantages and shortcomings are pointed out. This review can provide useful information for further academic research and industrial application.

    Research progress on utilization and systemic integration technologies of oil shale
    YANG Qingchun, ZHOU Huairong, YANG Siyu, QIAN Yu
    2016, 67(1):  109-118.  doi:10.11949/j.issn.0438-1157.20150819
    Abstract ( 147 )   PDF (622KB) ( 406 )  
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    Oil shale is an important unconventional energy resource and has enormous reserves. It is now considered as one of the most promising oil alternatives. A novel process integrated with oil shale retorting, oil shale/semi-coke combustion, shale oil and retorting gas upgrading and ash comprehensive utilization technologies, can increase energy efficiency and improve economic performance. This integrated process meets the needs of Chinese energy development strategy. It will have broad application prospects. A comprehensive overview of the key unit technologies and systemic integrated processes of the oil shale exploration and exploitation are presented. It can provide theoretical and technical foundations for the effective and environmental development of oil shale resource.

    Core technology in chemicals green manufacturing: synthetic biology
    XIAO Wenhai, WANG Ying, YUAN Yingjin
    2016, 67(1):  119-128.  doi:10.11949/j.issn.0438-1157.20151033
    Abstract ( 228 )   PDF (4248KB) ( 668 )  
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    Synthetic biology is the engineering of biology. Because it breaks the boundary of inanimate chemicals and life matter, and also promotes life science from understanding to creating, the synthetic biology has played a disruptive role in the development of science and technology, leading to great changes in chemical green manufacturing. Synthetic biology, as a core technology in chemical green manufacturing, mainly focuses on the design and optimization from raw materials to chassis and then the whole process. From the raw materials diversity, chemicals production and chassis selection aspects, the key role of synthetic biology in the chemical green manufacturing process, and also systematically elaborated the design and construction of artificial systems were summarized in this paper. In terms of feedstock, host cell and process, three aspects of outlook on how to develop synthetic biology to promote chemicals green manufacturing in the future were also proposed.

    Advances in production of important platform chemicals by bio-manufacturing based on systems biology and synthetic biology
    YUAN Haibo, LI Jianghua, LIU Long, DU Guocheng, CHEN Jian
    2016, 67(1):  129-139.  doi:10.11949/j.issn.0438-1157.20151042
    Abstract ( 137 )   PDF (2028KB) ( 660 )  
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    Due to the limited amount of fossil fuels and global warming problem, bio-manufacturing based on renewable biomass has been paid more attention. In this review, the contribution of systems biology and synthetic biology in bio-manufacture of platform chemicals like organic acid such as succinate, fumarate, malate, glucaric acid, pyruvate, phenylpyruvic acid, α-ketoglutarate and other platform chemicals such as 2,5-furandicarboxylic acid are reviewed. Finally, the trends of bio-manufacture for platform chemical are prospected.

    Adsorptive protein chromatography with grafted polymeric ligands
    YU Linling, SUN Yan
    2016, 67(1):  140-151.  doi:10.11949/j.issn.0438-1157.20151120
    Abstract ( 110 )   PDF (1145KB) ( 206 )  
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    Adsorptive protein chromatography, mostly based on ion exchange, affinity binding and hydrophobic interactions, is the key technology in the large-scale production of therapeutic proteins. The development of novel technology as well as improvement of chromatographic separation efficiency, such as dynamic binding capacity and selectivity, is generally the main objective of fundamental studies on protein chromatography. Recently, polymeric ligand-modified matrices have been developed and widely studied due to the findings that some of them not only possess high equilibrium adsorption capacity but also high uptake rate. This review is devoted to an overview of the polymeric ligands for protein chromatography. Different kinds of polymeric ligands are first introduced. This is followed by the effects and functional mechanisms of the polymeric ligand chemistry on protein adsorption equilibria, uptake kinetics as well as separation performance of the ligand-modified matrices. Applications of the matrices based on the mechanisms are then illustrated to offer insight into the design of new polymeric ligands. Finally, a perspective for further development and fundamental studies on polymeric ligand-based protein chromatography is discussed.

    Research progress on intermolecular weak interaction in extraction and separation system
    HUANG Kun, LI Xiaopei, XU Yizhuang, LIU Huizhou
    2016, 67(1):  152-164.  doi:10.11949/j.issn.0438-1157.20150999
    Abstract ( 167 )   PDF (462KB) ( 379 )  
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    The extraction reaction and separation in most cases occur on liquid-liquid interface, and generally, the formation of a new phase and phase-separation kinetics in extraction systems depend on step-by-step evolution of molecular aggregates in solution microstructure. Therefore, the research on various intermolecular interaction appeared in solutions or on the interface of contacting liquid phases during extraction and separation process, and exploration about the influence from the change, interrelationship and synergistic effect of those intermolecular interactions are becoming one of the research focuses and frontier around the world in current separation sciences and chemical engineering. It is very important towards understanding the microscopic mechanism in the separation process, and also how to control the separation selectivity. In present paper, recent research progress and some typical works about the intermolecular interaction on the interfaces of liquid phases, and various experimental techniques and methods employed to describe the intermolecular weak interaction in extraction and separation systems are reviewed.

    Progress of research on diffusional transport of heavy oil in pores
    CHEN Zhentao, XU Chunming
    2016, 67(1):  165-175.  doi:10.11949/j.issn.0438-1157.20151039
    Abstract ( 151 )   PDF (430KB) ( 266 )  
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    Intraparticle diffusion is a crucial factor for heterogeneous catalytic processes. Heavy oils are significantly influenced by diffusional transport in catalyst, which reduces the efficient conversion of the feedstocks and the effective utilization of the catalyst. An overview of the methods (diaphragm diffusion cell, adsorptive uptakeand reactive kinetic methods) and advances in diffusivity of heavy oils in pores is presented. Key factors of diffusion of heavy oils, such as temperature, concentration, molecular configuration and catalyst deactivation are discussed. At last, the directions of future development indiffusion of heavy oils are suggested.

    Progress in research of mitochondrial fluorescence probes
    JIANG Na, FAN Jiangli, YANG Hongbao, PENG Xiaojun
    2016, 67(1):  176-190.  doi:10.11949/j.issn.0438-1157.20151007
    Abstract ( 311 )   PDF (21409KB) ( 1612 )  
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    The researches on organelles are important ways to study the structure and function of cells. Mitochondria, the principal energy-producing compartments in most cells, play roles in the numerous vital cellular processes. Thus, the organelles are crucially involved in various pathologies. As one of the most important cellular organelles, mitochondria are always the focus of researches. There are three kinds of mitochondrial fluorescence probes. This paper mainly introduces and discusses the progresses of mitochondrial staining kind of fluorescent probes in recent 10 years on the basis of the fluorophore with positive charge or the introduction of positioning groups such as triphenylphosphine.

    Research progress on fluorescent probes for fluoride ions
    ZHANG Shiling, PENG Xiaojun
    2016, 67(1):  191-201.  doi:10.11949/j.issn.0438-1157.20150954
    Abstract ( 236 )   PDF (8270KB) ( 725 )  
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    Fluoride ions play an important role in many chemical, biological, medical and military processes because of strongest electronegativity, the smallest ion radius, and strong Lewis base. Low levels of fluoride ions have shown to be effective for prevention of dental caries and treatment of osteoporosis. But high concentration of fluoride intake is harmful to human body. It may cause dental fluorosis, skeletal fluorosis, urolithiasis and diseases such as cancers. Therefore, the recognition and detection of fluoride ions is of great significance. Fluoride fluorescent probes have attracted a wide spread attention due to its high selectivity and sensitivity, speediness and convenience, low cost, etc. In recent years, the researchers designed and synthesized a large number of fluorescent probes for fluoride ions. According to detection mechanism, fluorescent probes for fluoride ions mainly contained three types: 1) the hydrogen bond type; 2) Lewis acid style; and 3) the hydrogen bond and Lewis acid mixed. In this paper, the research progress of different types of fluorescent probes for fluoride ions respectively was reviewed, the advantages and disadvantages of different types were summed up, and the future research of fluorescent probes for fluoride ions was prospected.

    Progress in stimuli-responsive smart hydrogels with rapid responsive characteristics
    LIU Zhuang, XIE Rui, JU Xiaojie, WANG Wei, CHU Liangyin
    2016, 67(1):  202-208.  doi:10.11949/j.issn.0438-1157.20151015
    Abstract ( 210 )   PDF (4736KB) ( 901 )  
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    Stimuli-responsive smart hydrogels have been considered to be highly potential in versatile applications in numerous fields, such as chemical sensors and/or actuators, chemical values, artificial muscle, controlled drug delivery systems and substance separations, for which rapid responsive characteristics are highly desired. Therefore, rapid response to environmental stimuli is critical for the versatility of such smart hydrogels. This review briefly introduces the design and fabrication of stimuli-responsive smart hydrogels with rapid responsive characteristics, including three main types of smart hydrogels designed with different structures, which are open-cell porous structure, comb-type structure, and microsphere-composited structure. This review provides valuable information and guidance for rational design of novel stimuli-responsive smart hydrogels with rapid responsive characteristics.

    Structure and hydrodynamics characteristics of fluids under nano-confinement
    XU Junbo, WANG Yuying, YANG Chao
    2016, 67(1):  209-217.  doi:10.11949/j.issn.0438-1157.20150989
    Abstract ( 230 )   PDF (517KB) ( 609 )  
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    The fluids under nano-confinement show broad application prospect in membrane separation, mesoporous catalyst, etc., benefiting from the specific phenomena occurring at this small scale compared with that at macro scales. The layered and ordered structure of the fluids near the wall and its effect on the hydrodynamic characteristics of the fluids are the main differences from those at macro scales. The common rule of the molecules aggregation structure and the electric double-layer structure of fluids under nano-confinement, and their effects on the self-diffusion property and wall slip phenomenon are reviewed. The applicability of the macroscopic continuum theory in fluids under nano-confinement is discussed. Finally, future development of fluids hydrodynamics under nano-confinement is envisaged.

    Controlled synthesis and properties of gradient copolymers
    GUO Yunlong, LUO Yingwu
    2016, 67(1):  218-230.  doi:10.11949/j.issn.0438-1157.20151043
    Abstract ( 128 )   PDF (1528KB) ( 482 )  
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    Gradient copolymer is a new kind of polymers emerging with the living polymerization techniques. The unique structural feature is the gradual variation of monomeric compositions along the polymeric chains, distinguishing from random and block copolymers. The current paper reviews the preparation techniques, characterization methods, physical properties and potential applications of gradient copolymers. Kinetic model-based monomer feeding policy in controlled/living radical polymerization presents a sophisticated method to precisely synthesize gradient copolymers by design, while many-shot monomer feeding policy in RAFT emulsion polymerization is a facile and efficient technique to tailor-make compositional gradient copolymers. Compared random and block copolymers, gradient copolymers exhibit different self-assembly behaviors in both solution and bulk, resulting in unique interfacial, thermal and mechanical properties. Composition gradient is expected to be a new parameter to finely tune the properties of polymers. Gradient copolymers have shown promising applications in the phase compatibilizers, damping materials and multi-shape memory materials.

    D-A-π-A Featured sensitizers for organic solar cells with improved spectral response and stability
    WU Yongzhen, ZHANG Weiwei, ZHU Weihong
    2016, 67(1):  231-239.  doi:10.11949/j.issn.0438-1157.20151026
    Abstract ( 169 )   PDF (5651KB) ( 407 )  
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    Organic functional dyes have been widely exploited in optoelectronic fields. As a key element in dye-sensitized solar cells (DSSCs), their light-responsive spectral characters and long-term stability are the key issues on their practical applications. Generally, many traditional organic sensitizers are derived from the common concept of electron donor-π bridge-electron acceptor (D-π-A). Due to the finite donors and acceptors, the D-π-A model always exhibits limitation to the spectral response, photovoltaic efficiency and enduring stability. Recently, a novel D-A-π-A model via inserting an additional electron acceptor unit into the π bridge was proposed, allowing the convenient modulations in energy levels and light-harvesting. In this paper, the spectral modulation and stability enhancement based on D-A-π-A motif organic sensitizers were introduced.

    Advances in indirect synthesis of ethanol from syngas via dimethyl ether/methyl acetate
    HUANG Shouying, WANG Yue, LÜ Jing, ZHAO Yujun, WANG Shengping, MA Xinbin
    2016, 67(1):  240-247.  doi:10.11949/j.issn.0438-1157.20151294
    Abstract ( 147 )   PDF (976KB) ( 564 )  
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    Ethanol, as an important clean energy, can be used for fuel alternative or additive, which has a huge market potential. Recently, a novel indirect synthesis route of ethanol from syngas via carbonylation of dimethyl ether followed by hydrogenation of methyl acetate has attracted much attention. The route possesses several advantages such as high selectivity, mild reaction conditions, cheap catalysts as well as no poisonous emission, which accord with the principles of green chemistry. In addition, the absence of ethanol-water binary azeotrope in products significantly reduces the cost of separation. This review focuses on recent advances in the two key step (carbonylation and hydrogenation), especially in development of catalyst and catalysis mechanism. The progress of this route will promote clean and diversified development of energy in China.

    Ionic liquids based membranes for CO2 separation: a review
    BAI Lu, ZHANG Xiangping, DENG Jing, LI Mengdie
    2016, 67(1):  248-257.  doi:10.11949/j.issn.0438-1157.20151462
    Abstract ( 402 )   PDF (460KB) ( 876 )  
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    Ionic liquids (ILs) have been widely used for CO2 separation because of their unique properties, such as negligible vapor pressure, tunability for aimed application and high solubility for CO2. However, the high viscosity and pricey cost of ILs limit their use in industrial applications. Thus, immobilization of ILs in membranes becomes one of the hot research spots in IL field due to the ILs based membranes possess both the advantages of ILs and membranes. This review summarizes the latest research on supported ionic liquid membranes, polymerized ionic liquid membranes and ionic liquid composite membranes for CO2 separation. It is also discussed how the structures of ILs and ILs contents influence on the gas separation performances and stabilities of membranes. The research indicates that ILs composite membranes have high separation performance and stability, which is one of the prospective materials for CO2 capture. The future research should highlight on the development of the novel fuctionalized ILs composite membranes and the trade-off of high CO2 permeation rate and high stability to enhance the CO2 separation performance. Besides, the study on the fabrication of composite membrane, gas transportation in membrane and CO2 separation mechanism will inevitably attract considerable attentions.

    Acid-base synergistic effect promoted cycloaddition reaction from CO2 with epoxide in homogenous catalysis systems
    LUO Rongchang, ZHOU Xiantai, YANG Zhi, ZHANG Wuying, JI Hongbing
    2016, 67(1):  258-276.  doi:10.11949/j.issn.0438-1157.20150749
    Abstract ( 190 )   PDF (1430KB) ( 506 )  
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    In terms of the so-called “sustainable society” and “green chemistry” concepts, carbon dioxide capture, storage and utilization have been attracted much attention from both industrial and academic viewpoints in recent years. The synthesis of five-membered cyclic carbonates via the 100% atom-economical cycloaddition of epoxides with CO2 under mild condition is one of the most promising ways. Herein, based on the design idea of homogenous catalysts, the research advance of the acid-base synergistic effect promoted the cycloaddition reaction from CO2 and epoxide is reviewed from the perspective of catalyst structure, including simple binary catalytic systems, functionalized one-component catalytic systems and metal complexes catalytic systems etc.

    Advances in enzyme stability modification
    FENG Xudong, LÜ Bo, LI Chun
    2016, 67(1):  277-284.  doi:10.11949/j.issn.0438-1157.20151025
    Abstract ( 165 )   PDF (13511KB) ( 656 )  
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    Enzymes play an increasingly important role in diverse industrial fields such as food, pharmacy and fine chemistry. However, most of the enzymes require mild reaction conditions to maintain the activity, and they have poor tolerance towards heat, acid and salt under stressful conditions in real applications. Thus, the enzymes are very labile to lose their activity, severely limiting their applications. Therefore, it is critical and also challenging to engineer enzymes for higher stability. In this paper, the progress in enzyme stability modification is summarized from perspectives of chemical decoration and molecular modification. The molecular modification is illustrated with regards to directed evolution, semi-rational, ration design and glycosylation, where the glycosylation as a new tool to improve enzyme stability is briefly reviewed.

    Design and application of energy optimization system in petrochemical enterprise
    LI Defang, JIANG Baihua, SUO Hansheng, LIU Xuan
    2016, 67(1):  285-293.  doi:10.11949/j.issn.0438-1157.20151455
    Abstract ( 99 )   PDF (2059KB) ( 363 )  
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    Petrochemical industry is a high energy consumption area, its development is being restricted by the shortage of resources. Energy management system based on the deep integration of informatization and industrialization can greatly improve the quantitative management abilities of energy and has a great prospect on supporting an enterprise to optimize its energy consumption. Sinopec achieves satisfactory results by constructing energy management system based on information technology. The overall planning of energy optimization system has been proposed in this paper, the functions of this system have been designed by analyzing petrochemical businesses. Moreover, the steam power system has been taken as an example to illustrate the business functions of the optimization system. The specific description of energy optimization process of the system has been demonstrated in the aspects of the construction of mechanism factory model, data inspection, data correction, online energy optimization and online model regulation. Finally, the application benefits of three pilot enterprises have been analyzed. Especially, this can be regarded as a reference provided for petrochemical enterprises to promote energy conservation in their informatization construction process.

    Acetylene dimerization catalyzed by Nieuwland catalyst
    ZHANG Yike, JIA Zekun, ZHEN Bin, HAN Minghan
    2016, 67(1):  294-299.  doi:10.11949/j.issn.0438-1157.20150894
    Abstract ( 179 )   PDF (432KB) ( 321 )  
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    Acetylene dimerization catalyzed by Nieuwland catalyst for the production of monovinylacetylene (MVA) is the crucial step for the manufacture of chloroprene from acetylene. The influence of the additives, DL-alanine content, acetylene gas hourly space velocity and internal diameter of the gas distributor on the reaction process were investigated. In addition, a continuous two-stage dimerization reaction was carried out. The result showed that DL-alanine would induce lower acetylene conversion and higher MVA selectivity. Higher acetylene gas hourly space velocity would cause shorter apparent residence time and strong back-mixing, which led to lower acetylene conversion and MVA selectivity. Small internal diameter of gas distributor favored the enhancement of mass transference through gas-liquid interface and the attenuation of back-mixing, which induced both high acetylene conversion and high MVA selectivity. In a continuous two-stage reaction process, both acetylene conversion and MVA selectivity kept in a high level. When the gas hourly space velocity of acetylene was 100 h-1, the acetylene conversion and MVA selectivity were 32.5% and 95.3%, respectively.

    Adsorption equilibrium and mechanism of ethanol on MIL-101(Cr)
    YU Ying, SUN Xuejiao, YAN Jian, XIAO Jing, XI Hongxia, LI Zhong
    2016, 67(1):  300-308.  doi:10.11949/j.issn.0438-1157.20151052
    Abstract ( 289 )   PDF (1665KB) ( 519 )  
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    The adsorption performance and adsorption mechanism of ethanol on MIL-101(Cr) were investigated. MIL-101(Cr) was synthesized using a hydrothermal synthesis method, and characterized using N2 adsorption measurements, powder X-ray diffraction, and Fourier transform infrared spectroscopy. The adsorption isotherms of ethanol and water vapor were measured by static adsorption method at different temperatures, and ethanol adsorption mechanisms on four types of adsorptive sites in MIL-101 were discussed. The isosteric heats of ethanol and water adsorption were calculated according to these isotherms. The adsorption and desorption of ethanol on MIL-101 were evaluated. Results show that adsorption capacity of MIL-101(Cr) for ethanol is up to 20.3 mmol·g-1 at 298 K, much higher than those of some traditional adsorbents. At low pressure, the adsorption capacity of MIL-101 for ethanol is higher than that for water vapor, which could be ascribed to larger dipole moment and dynamic diameter of ethanol compared to water molecule. In addition, the isosteric heat of ethanol adsorption on MIL-101 is higher than that of water vapor adsorption. At high pressure, multilayer adsorption or cage filling occurs, so the molecule with large dynamic size will fill within MOFs with less moles than that with small dynamic size due the limitation of pore volume of MOFs. As a consequence, the adsorption capacity of MIL-101 for ethanol is lower than that for water vapor because the dynamic diameter of ethanol (0.45 nm) is larger than that of water molecule (0.268 nm). The ethanol adsorption and desorption isotherms show that ethanol adsorption on MIL-101 is highly reversible.

    Influence of aqua-ethanol medium on properties of intermediate layer ofa bipolar membrane
    LIU Xiaohe, LI Qiuhua, GE Liang, XU Tongwen
    2016, 67(1):  309-314.  doi:10.11949/j.issn.0438-1157.20151004
    Abstract ( 97 )   PDF (533KB) ( 335 )  
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    A bipolar membrane (BPM) was composed of a cation and an anion ion-exchange layer joined together in series. The water dissociation in BPM was then considered as an electric field-enhanced (EFE) phenomenon and its magnitude depended critically on the structure and composition of the bipolar intermediate layer. By changing the different content of ethanol, three commercial bipolar membranes Neosepta BP-1, Fumasep FBM and CJ-BPM were tested by AC impedance spectra and their bipolar membrane solvent resistance were evaluated simultaneously. It was confirmed that BP-1 had good solvent resistance and FBM and CJ-BPM solvent resistances were relatively weak. The experimental results showed that the water dissociation phenomenon occurred in the LiCl water-ethanol mixed solutions, and the local effective value of the BPM resistance increased with an increase in the content of ethanol, while the water dissociation became less obvious. This phenomenon could be explained due to the fact that the dissociative ability of alcohol was weaker than that of water. Thus, the existence of ethanol decreased the concentration of water in the intermediate layer of a bipolar membrane and caused the decrease in the water dissociation effect. By simplifying the algorithm to calculate the intermediate layer thickness of the BP-1 and FBM membranes, it was more intuitive to know the influence of ethanol content on the water dissociation.

    Combinatorial design and construction of artificial yeast for production of taxadien-5α-ol
    ZHAI Fang, SONG Tianqing, XIAO Wenhai, DING Mingzhu, QIAO Jianjun, YUAN Yingjin
    2016, 67(1):  315-323.  doi:10.11949/j.issn.0438-1157.20150992
    Abstract ( 127 )   PDF (1691KB) ( 403 )  
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    Producing natural drugs such as Taxol by engineered microbes have attracted extensive attention in recent years. This work focused on how to design and construct artificial yeast for the production of taxadien-5α-ol, which was the first hydroxylated product catalyzed by cytochrome P450 enzymes in Taxol biosynthesis pathway. Based on combinatorial design, three hydroxylase genes derived from different yew subspecies and two reductase genes from different organisms with N-terminal truncatd with various length were tested simultaneously to investigate the fitness between the genes and the chassis. Two kinds of promoters were used for regulating the cytochrome P450 reductase genes. In total, 72 kinds of combinations were constructed and then integrated into the chromosome of the taxadiene producing strain. 48 taxadine-5α-ol producing strains were obtained out of 72 combinations by co-expression of the hydroxylase and the reductase. The highest titer was 67.3 μg·L-1. This was the first time to realize the biosynthesis of taxadine-5α-ol form glucose in Saccharomyces cerevisiae. The result provided a good reference for the research of the catalytic reaction mediated by cytochrome P450 enzymes in microbes through the interactions between modules and chassis by combinatorial design.

    Prediction of lipid yield and substrate distribution based on consumed C/N ratio
    SHEN Hongwei, YANG Xiaobing, GONG Zhiwei, JIN Guojie, ZHAO Zongbao
    2016, 67(1):  324-330.  doi:10.11949/j.issn.0438-1157.20150454
    Abstract ( 96 )   PDF (446KB) ( 255 )  
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    Microbial lipids, similar to vegetable oil in their composition, are potential alternative feedstock for biodiesel production and oleochemical industries as well. However, the high costs of microbial lipids production are the major bottleneck. The synthesis of microbial lipids is considered as a partially growth-associated process with inconstant production rates. For the prediction of lipid yield and substrate distribution, a chemostat process was established for lipid production by the oleaginous yeast Rhodosporidium toruloides AS 2.1389 under nitrogen limitation conditions, and a correlation on carbon distribution between lipid and lipid-free cell components was also developed. The maximal lipid yield YLmaxand cell mass yield YLmaxwere predicted to be 0.51 mol C·(mol C)-1 and 0.52 mol C·(mol C)-1, respectively. Together with the element balance analysis, the critical C/N ratio for switching to lipid production was estimated to be 12.1 mol·mol-1. The prediction for lipid yields was 95.2%—116.7% of those measured experimentally, indicating that the model was reliable.

    Preparation of alkyl chain cross-linked sulfobutylated lignin and its application in dispersion of carbon nanotubes
    ZENG Weimei, LI Yuan, LI Yuda, DENG Yonghong, QIU Xueqing
    2016, 67(1):  331-338.  doi:10.11949/j.issn.0438-1157.20151035
    Abstract ( 120 )   PDF (1956KB) ( 319 )  
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    Using 1,4-butane sultone as a sulfonating agent and C6H12Br2 as an alkyl chain cross-linking agent, a new family of water soluble alkyl chain cross-linked sulfobutylated lignosulfonates (AASLS) was readily prepared by one step reaction in water, which simultaneously improved sulfonation degree and molecular weight. FTIR, 1H NMR, functional group content tests and GPC confirmed their cross-linked chemical structure and efficient nucleophilic substitution reaction mechanism. The dispersion properties of AASLS-carbon nanotubes (CNT) suspension system were systematically studied. The results showed that when the dosage was 2% (mass), AASLS-CNT suspensions had a higher absorption at 660 nm with a higher suspension stability than that in polyvinyl pyrrolidone (PVP) and sodium polystyrene sulfonate (PSS). Moreover, the transmission electron microscopy (TEM) indicated that the incorporation of AASLS could effectively solve the problem of the agglomeration of CNT. The Raman absorption spectra showed that the I1350/I1580 value of CNT was effectively reduced by the non-covalent functionalization of AASLS, showing that the density of surface defects was decreased. In cyclic voltammogram (CV) test of AASLS-CNT, it was found that AASLS-CNT showed the quasi reversible redox behaviors.

    Development and experimental validation of fractal char particle combustion model with effect of various reaction order
    LIU Yuting, HE Rong
    2016, 67(1):  339-348.  doi:10.11949/j.issn.0438-1157.20150934
    Abstract ( 136 )   PDF (574KB) ( 233 )  
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    A fractal char particle combustion model was developed to study the char combustion mechanism and improve the prediction accuracy of the char combustion characteristics. This model considered the coupling effects of the secondary reactions and gas diffusion within the char pores. The apparent reaction order of char combustion changed with the particle temperature, the O2 partial pressure at the particle surface and the particle pore structure parameters instead of keeping constant 1. The primary CO/CO2 ratio was obtained by theoretical derivation. The combustion characteristics of eleven different chars were analyzed by a thermogravimetric analyzer (TGA) with their apparent activation energies and pre-exponential factors measured which were used to solve the undetermined model parameters. These chars were also combusted in a drop tube furnace (DTF) and the char samples were collected at the outlet of the DTF. The conversions of these char samples were measured by TGA based on the ash conservation method. The combustion processes of these chars were simulated by this model. The predicted char conversions by this model were matched very well with the measured data and the accuracy was significantly improved compared with the intrinsic model, proving that this model had good accuracy over a wide range of char particles from lignite to anthracite. The study also showed that the apparent reaction order of char combustion first decreased and then gradually stabilized in the char combustion process.

    Dynamic adsorption-desorption of nickel or cadmium from metallurgical wastewater by nanoscale humic acid based ion exchange composite resin
    CHENG Liang, HOU Cuihong, XU Li, LIU Wei, LUO Tingliang, ZHANG Baolin, LIU Guoji
    2016, 67(1):  349-357.  doi:10.11949/j.issn.0438-1157.20151186
    Abstract ( 72 )   PDF (938KB) ( 252 )  
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    The selective adsorption performance of nanoscale humic acid based ion exchange composite resin for Ni2+/Cd2+ was investigated from multi-ionic co-existing system. On this basis, a novel resource recovery process for Ni/Cd wastewater, which included multi-column series, saturated adsorption and concentrated circulation, was developed. The micro-morphology, chemical structure, heat resistance, element composition change and pore size distribution of nanoscale humic acid based ion exchange composite resin were characterized by SEM, FTIR, TG-DTG, XPS and BET. The experimental results showed that the ion exchange composite resin had the advantage of fast adsorption rate [0.55—1.50 mg·(g·min)-1], high exchange capacity(139 or 148 mg·g-1 for Ni2+/Cd2+ on Ca2+ and Mg2+ coexisting system)and excellent selectivity behavior, high elution concentration and purity for Ni2+/Cd2+ (45.15 g·L-1 or 39.17 g·L-1, and QNi(Ⅱ)/Qtotal 0.989,QCd(Ⅱ)/Qtotal 0.994). After 200 adsorption-regeneration cycles, the physical and chemical structures of the adsorptive composite resin were still kept stable performance, and the section morphology and exchange capacity basically remain unchangeable, showing that it can be reused. The specific surface area, average pore diameter and pore volume were 1189.85 m2·g-1, 30.2 nm and 0.96 cm3·g-1, respectively with good thermal stability. The nitrogen content decreased from 16% to 12%, oxygen content increased from 26.49% to 29.96% and ionic exchange capacity rose from 5.38 mmol·g-1 to 6.06 mmol·g-1.

    Preparation and characterization of proton exchange membranes based onsulfonated poly(ether ether ketone) doped with phosphorylated mesoporoussilica submicrospheres
    WU Hong, YANG Hao, ZHAO Yuning, LI Zhen, JIANG Zhongyi
    2016, 67(1):  358-367.  doi:10.11949/j.issn.0438-1157.20150520
    Abstract ( 211 )   PDF (1551KB) ( 427 )  
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    Two kinds of phosphorylated mesoporous silica submicrospheres were prepared. The phosphoric acid groups ( PO3H2) were grafted either only on the particle outer surface (PMPS-Ⅰ) or on both the outer surface and the inner pore walls (PMPS-Ⅱ). All the submicrospheres exhibited a uniform particle size and possessed well-aligned one-dimensional hexahedral pores. Hybrid membranes were fabricated by directly blending silica with the sulfonated poly(ether ether ketone) (SPEEK) solutions. The hybrid membranes doped with PMPS-Ⅱ exhibited higher proton conductivity compared to the ones with PMPS-Ⅰ. The highest proton conductivity was 0.241 S·cm-1 at 60℃ and 100% relative humidity (RH) for the hybrid membrane with 5% (mass) of PMPS-Ⅱ. The experimental results indicated that continuous proton conduction channels were advantageous for the enhancement of proton conductivity of the hybrid membranes.