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Table of Content
25 February 1988, Volume 39 Issue 1
    化工学报
    Reactive Disperse Dyes for Synthetic PolymerFibres and their Natural Fibre Blends(III) The Dyeing Mechanism of Reactive DisperseDyes with β-Hydroxy-Ethyl Sulfonyl SulfuricEster Group for Polyester-Cotton Blend
    Zhang Yingju and Hou Yufen (Chemical Engineering Department, Dalian Institute of Technology, Dalian)
    1988, 39(1):  1-10. 
    Abstract ( 603 )   PDF (520KB) ( 222 )  
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    The migration behavior of reactive disperse dyes containing β-hydroxy-ethyl sulfonyl sulfuric ester group at different stages of dyeing and the ther-mofixation on the polyester-cotton blend were thoroughly investigated. The sublimation properties of the dyes were examined and the diffusive process of dyes in the vapor phase during thermofixation was identified. It was concluded that thermofixation conditions would effect the dye distribution in the cotton and polyester portions in the blend. The relationship between the dye molecule structures with respect to their distribution in the cotton and polyester portions was established. A dyeing mechanism of reactive disperse dyes for polyester-cotton blend was outlined and discussed.
    A New Correlation for the Transport Disengaging Height (TDH) of Fluidized Bed
    Xie Yusheng, Qin Jiguang, Li Qi and Zhang Heng (Institute of Chemical Metallurgy, Academia Sinica) (Research Institute of Chemical Machinery, Ministry of Chemical Industry)
    1988, 39(1):  11-19. 
    Abstract ( 860 )   PDF (433KB) ( 295 )  
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    In the design of fluidized-bed units, determination of TDH (Transport Disengaging Height) for the dilute-phase zone appears to be of primary importance. Presently, the empirical curve developed by Zenz and Weil in 1958 has been widely used. In the present paper, taking the equation for the motion of single particles as the basic starting point, methods for calculating gas velocity, particle velocity, and particle stagnation time and rising height in gas-solid flow, have been developed through theoretical analysis, resulting in an eight-parameter expression, Equation(15), for computing TDH. This equation includes more parameters than given in any previous work, and conforms much better with experimental results. It is, henceforth, recommended for design work.
    Relationship Between The Structure of Networks and The Mechanical Properties of Rubber Vulcanizates(I) Rubber Elasticity Theory for Vulcanizates with Carbon Black Fillers Presenting Extensive Deformation
    Song Mingshi (Department of Applied Chemistry, China University of Science and Technology, Hefei)
    1988, 39(1):  20-31. 
    Abstract ( 508 )   PDF (596KB) ( 108 )  
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    The fluctuation of chains and junctions in real vulcanizates with carbon blacks tended to be suppressed by the presence of three kinds of forces, namely network, trapped entanglement and carbon-polymer interaction forces. A new molecular theory of rubber elasticity, concerning the constraints of junctions, trapped entanglement and carbon-polymer interactions, was presented. It was then possible to relate the elastic equation of state to the molecular constitution through three important quantities (C100, C200 and C020). The severity of junction, trapped entanglement and carbon black-polymer interaction constraints could thus be characterized by four molecular para-meters(ΦΔc, ΦΔe, ΦΔcf and ΦΔef). A structural model of constituent chains and networks for vulcanizates with carbon blacks was proposed. The four constituent chains were taken as statistically elementary unit for network assembly. They were also considered as independent elementary unit taking part in the macroscopicdeformation. The ultimate networks were formed by the combination of three different kinds of networks, namely crosslinked, trapped entanglement and carbon black polymer chain networks. It was shown that the probability distribution functions of end-to-end vector for the four kinds of constituent chains mentioned above were different from the Gaussian function. Using the probability distribution functions and the proposed mechanism of large deformation, we have calculated the elastic free energy of deformation as the sum of two terms, one from the crosslink-entanglement networks and the other from the carbon black-polymer chain networks. The expression of the elastic free energy of deformation for vulcanizates with carbon black fillers was given in Equation(20). The relationship of stress and strain for four different types of deformation (uniaxial extension, equi-biaxial extension, unequi-biaxial extension and pure shear) were derived from the theory of elasticity for vulcanizates with carbon black fillers. These were given in Equation(21), (22), (23)and(24), respectively.
    Relationship Between The Structure of Networks and The Mechanical Properties of Rubber Vulcanizates (II) The Reinforcement of Elastomers by Carbon Black and Its Characteristics
    Song Mingshi and Zhang Huanzhi (Department of Applied Chemistry, Chin University of Science and Technology, Hefei)
    1988, 39(1):  32-43. 
    Abstract ( 609 )   PDF (612KB) ( 96 )  
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    A statistical theory of reinforcement and its charateristics were derived. The elastic free energy of deformation (ΔFTTT) and the retractive force(τ) for tilled rubber vulcanizates may be greater or small than the corresponding values for rubber vulcanized without carbon black, processed under similar conditions, three methods for the characterization of reinforcement were proposed. They were given in Equations (7) to(13). The effects of carbon black on the mechanical behaviors of SBR and NR vulcarmates were studied through uniaxial, equi-biaxial and unequi-biaxial extensions. Excellent agreement between experimental stress-strain Curves and computations with theoretical equations (3), (4) and(5) derivedfrom our proposed theory of elasticity was obtained. Apparently, the proposed theory served well for the prediction of rubberlike elasticity even at higher strains. Excess elastic free energy of deformation, excess retractive force and reinforcement strength for SBR and NR vulcanizates filled with carbon blacks were calculated with Equations(7),(8), (11)and(12). It was found that the physical and chemical properties of reinforcement increased linearly with increasing weight fraction of carbon black. A correlation between the structural parameters of C and the tensile strength for SBR vulcanizates filled with different grades of carbon blacks was obtained. It was also noted that the tensile strength increased with increasing values of parameters C100 and decreased with increasing values of C200/(C100 + C200).
    Employing Semicircular Electrode Pair to Measure Fluctuations of Velocity Gradients on the Wall
    Mao Zhuoxiong T. J. Hanratty (Institute of Chemical Metallurgy,Academia Sinice, Beijing) (Department of Chemical Engi- neering, University of Illinois,Urbana, Illinois, U. S. A. )
    1988, 39(1):  44-53. 
    Abstract ( 505 )   PDF (444KB) ( 168 )  
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    Measurement of turbulent velocity gradient on the wall is important for further understanding wall turbulence and mechanism of heat and mass transfer near the wall. This paper describes the principle of such a measurement, and a semicircular electrode pair is suggested for the measuring of the two dimensional fluctuations of velocity gradient on the wall. In a fully developed turbulent pipe flow, with pipe diameter of 0.194m and electrode pair diameter of 5 × 10-4m, using iodine-potassium iodide solution as fluid medium, the measured axial and transverse turbulent intensities of velocity gradients are 0.3-0.33 and 0.11-0.12 respectively.
    Economical Analysis and Optimization ofExtraction Purifying Processes for HighGrade Nickel Matte Sulfuric Acid Leaching Solutions
    Qu Delin, Yu Gingfen and Teng Teng (Qinghua University, Beijing)
    1988, 39(1):  54-63. 
    Abstract ( 480 )   PDF (432KB) ( 122 )  
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    Aiming at solving problems encountered in commercial hydrometailur-gical applications, a systematical process analysis was conducted on leaching solutions from a high grade nickel matte. Two extraction purifying processes of nickel and cobalt were experimented with Extractants 5709 and P507 and their performances were analysed, both technically and economically. Process simulation and design were based on models of extraction and stripping developed experimentally. It was concluded that the process flowsheet using Extractant 5709 appeared to be optimal. Optimal operational parameters and cost of individual unit operation were further obtained.
    Studies on the Vapor- Liquid Equilibrium and Vapor-Liquid-Liquid Equilibrium for a Methanol-Methyl Methacrylate-WaterTernary System (I) Three Different Binary Systems
    Fu Jinyan, Wang Kun and Hu Ying (Thermodynamic Research Laboratory, East China Institute of Chemical Technology, Shanghai)
    1988, 39(1):  64-76. 
    Abstract ( 671 )   PDF (610KB) ( 212 )  
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    Isothermal P-x data for binary systems of methanol-methyl methacryl-ate and methanol-vvater and isothermal P-xR-xR data for a binary system of methyl methacrylate-water have been determined at 25, 35, 45, 55, and 60℃. Based on the maximum likelihood principle, modified UNIQUAC model parameters for each binary system are thus obtained. Vapor compositions are then calculated. Results obtained are extensively compared with data found in literature.
    Studies on the Vapor-Liquid Equilibrium and Vapor-Liquid-Liquid Equilibrium for a Methanol-Methyl Met hacrylate-Water Ternary System (II) Ternary System
    Fu Jinyan,Wang Kun and Hu Ying (Thermodynamic Research Laboratory, East China Institute of Chemical Technology, Shanghai)
    1988, 39(1):  77-88. 
    Abstract ( 631 )   PDF (579KB) ( 156 )  
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    Isothermal P-x data of homogeneous mixtures and isothermal P-xE-xR data of partial miscible mixtures for a ternary system of methanol-methyl methacrylate-water have been determined at 25,35,45,55, and 60℃. Using a modified UNIQUAC model and binary parameters only, the predicted ternary phase equilibria data are in good agreement with experimental results. This indicates that these binary model parameters can be used as fundamental data for the calculation of the VLE and VLLE in this ternary system, covering low pressure to normal pressure situations.
    The Kinetics of NO Absorption into Aqueous Fe(II)-EDTA Solution
    Li Huasheng Fang Wenji (Zhengzhou Institute of Technology, Zhengzhou)
    1988, 39(1):  89-97. 
    Abstract ( 632 )   PDF (412KB) ( 217 )  
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    A process for the simultaneous absorption of NO (from nitric acid plant emissions) and H2S(from coal gas produced in synthetic ammonia plants) in aqueous Fe(II)-EDTA solution was proposed. The kinetics of absorption of NO in aqueous Fe(II)-EDTA solution was studied. It was found that the reaction was rather complicated: NO +Fe(II) - EDTA = Fe(II) (NO) EDTA, and was a second order reaction with respect to the forward reaction and first order with respect to the reverse reaction. The mechanism of the absorption process was discussed, the mathematical model describing the absorption process of(2,l)order fast reversible reaction: A + B = E, was established, and compared with other mathematical models describing the same system. Data from kinetic experiments of NO absorption in aqueous Fe(II)-EDTA solution correlated well with the mathematical model presented by the authors. The Marquardt Method was used to get optimum values for calculations. A kinetic equation of NO absorption in aqueous Fe(II)-EDTA solution was finally established.
    A Study on the Macro-Kinetics of Methane-Steam Reforming Reaction with Wheel Catalysts
    Xu Kaqiu, Wang Jianhua, Jiang Like and Su Yuguang (Chengdu Chemical Industry Research and Design Institute)
    1988, 39(1):  98-106. 
    Abstract ( 702 )   PDF (450KB) ( 237 )  
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    The macro-kinetics of methane-steam catalytic reforming reaction with wheel catalysts of original sizes was investigated in an internal recycling gradientless reactor (Type KD-1) under 3.04×106 Pa absolute pressure. Experimental conditions employed were as follows: reaction temperature 600-800℃, H2O/CH4 = 2.0-5.0 (molar ratio), carbon space velocities 4320-12120 ml/h. g. The methane-steam reforming reactions were described by parallel reaction models and experimental data were regressively computerized. The following macro-kinetics equations were obtained: and Calculations from experimental data indicated that water gas shift reaction is far away from equilibrium; wheel catalyst are about two times as effective as that of normal ring catalysts. Macro-kinetics equations thus obtained were applied on a commercial reformer; claiming reliability for the equations and good equivalence.
    The Effective Activity Layer of Spherical Pellet Catalysts
    Gu Qiwei and Ye Minghua (UNILAB Research Institute of Chemical Reaction Engineering, East China Institute of Chemical Technology (Branch) ,Shanghai)
    1988, 39(1):  107-112. 
    Abstract ( 592 )   PDF (255KB) ( 267 )  
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    An investigation on the formation of an effective activity layer by acetylene penetration in copper-bismuth catalyst with spherical silica gel as supporter was conducted in connection with butynediol synthesis. Employing Weisz-Prater Criterion, it was proved that, within the scope of our experimental conditions, acetylene was the key component in the bicomponent in-trapellet diffusion control system. Since acetylene showed zero order in intrinsic reaction kinetics, according to the criterion value 2A, valuable conclusions were drawn by comparing uniformed distributed copper with egg-shell and multilayer distributed catalyst pellets.
    Vortex Geometry in Self-Induction Gas-LiquidAgitated Vessels
    Chen Mingguang, Sun Jianzhong, Tang Furui, Gu Peiyun and Pan Zuren (Chemical Engineering Department, Zhejiang University, Hangzhou)
    1988, 39(1):  113-119. 
    Abstract ( 557 )   PDF (334KB) ( 202 )  
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    The vortex geometry and the radius of the cylindrical rotating zone in a vertical self-induction gas-liquid vessel with co-axial propeller agitation was formulated by the momentum balance method and verified by experimental investigations. From this, the critical inductive speed N and the variation of the cylindrical rotating zone with Reynolds number could be predicted. It was found that the propeller performed much better than other types of impellers such as flat blade impeller, flat blade turbine and flat blade disc turbine, because of its lower critical inductive speed and less effect of cylindrically rotating zone. Thus, it was claimed that such a propeller may be a good component for gas-liquid polymerization reactors.
    The Characteristics of a Biological Fluidized Bed in Magnetic Field
    Hu Zongding and Wu Jianyong (Tianjin University, Tianjin)
    1988, 39(1):  120-126. 
    Abstract ( 561 )   PDF (304KB) ( 290 )  
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    The object of this study is to observe the fluidization behaviour of liquid-solid and gas-liquid-solid fluidized beds with magnetic immobilized enzyme support particles as the solid phase in a uniform magnetic field. The voidage of the liquid-solid beds, the average gas holdup and the radial distribution of holdups of the gas-liquid-solid bed in magnetic fields were measured and correlated in empirical models. The fluidized bed in magnetic field was also used in an immobilized-cell catalized reaction system to test its applicability.