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  • Wiley-Blackwell  (4)
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 1251-1265 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A comprehensive kinetic model developed for molecular weight calculations of ethylene axsnd α-olefin copolymerizations in the context of a terminal model accounts for multiple-type active centers of the catalyst, detailed elementary chemical reactions, and catalyst composition. The moments of copolymer chain distributions are defined considering molecular weights of comonomer units so that copolymer molecular weight averages can be directly calculated from those moments. A double Z-transformation is introduced for the derivation of differential equations of the moments. Model simulations are carried out based on ethylene and 1-butene copolymerizations in a gas-phase fluidized-bed reactor. Polydisperity of accumulated copolymer depends on catalyst composition and kinetic characteristics of the catalyst. For a catalyst with specified kinetic characteristics, the polydispersity depends on the mole fraction of each type of active center. For a catalyst with two types of active centers, the maximum polydispersity of copolymer occurs at 50 wt. % of the total copolymer if polydispersities of the copolymers generated at each active site are the same. Polydispersity of accumulated copolymer is sensitive to propagation reactions and chain transfer to hydrogen reactions. Differences in chain transfer to cocatalyst and monomers and in spontaneous deactivation rates for different types of active centers may play minor roles in controlling molecular weight development in the presence of hydrogen. This model can be used for catalyst composition design, simulation of commercial olefin copolymerization processes, and kinetic parameter estimation.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2073-2082 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A one-dimensional nonequilibrium model for multicomponent condensation is used to simulate a vertical single-pass shell-and-tube heat exchanger in an industrial gas-phase polyethylene reactor system. Starting the calculation at the top of the exchanger, the model can predict temperatures at the bottom of the exchanger within an accuracy of ±5 K as compared to three sets of industrial data. Sensitivities of model predictions were analyzed, including uncertainties associated with physical and transport property estimates, step size, and convergence criterion. Model predictions are not particularly sensitive to the estimation errors of physical and transport properties if K values are calculated using an equation of state applicable to both liquid and vapor phases. Effects of operating conditions on heat removal from polyethylene reactors were investigated for an existing process. It was quantitatively demonstrated why and how severely noncondensable gases impede condensation heat transfer. The level of noncondensable gases and the cooling water temperature are the two most important factors influencing the heat-removal rate. Replacing a portion of noncondensable gas, such as N2, with a condensable fluid that is inert to polymerization reactions can substantially increase the heat-removal rate from the reactor, thereby allowing for an increase in polymer production rate.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2965-2970 
    ISSN: 0887-624X
    Keywords: lactide ; polymerization ; mechanism ; alcohol ; carboxylic acid ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of hydroxy and carboxylic acid substances on lactide polymerization in the presence of stannous octoate was investigated. A polymerization mechanism was postulated to attempt to explain the controversies existing in the literature and also to explain our experimental observations. Stannous alkoxide, a reaction product between stannous octoate and alcohol, is proposed as the substance initiating the polymerization through coordinative insertion of lactide. Alcohol can affect the polymerization through the reactions of initiator formation, chain transfer, and transesterfication. Carboxylic acid affects the polymerization through a deactivation reaction. Experiments showed that alcohol increased PLLA production rate while carboxylic acid decreased it. Both alcohol and carboxylic acid reduced PLLA final molecular weight. The higher the alcohol concentration, the lower the polymer molecular weight. However, the final molecular weight of PLLA was not sensitive to the carboxylic acid concentration. A polymerization induction period was observed at high carboxylic acid concentration, due to the deactivation reaction caused by carboxylic acid. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 13-24 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In most industrial gas-phase polyethylene reactors, heat is removed by cooling the recycle gas stream in an external heat exchanger, where a portion of the vapor is condensed. The condensate evaporates in the reactor to absorb heat released by polymerization reactions, thereby increasing the production capacity of the unit. Nonequilibrium methods of multicomponent condensation are applied to develop a 1-D model to simulate the cooling unit of an industrial polyethylene reactor system operated in partial condensing mode. Finite difference approximations are used to convert the resulting set of differential equations to algebraic equations. A practical method of solving the equations is to combine the rapid local convergence of Newton's method with a globally convergent strategy. Correlation methods for estimating local heat-transfer coefficients in the liquid film layer are discussed. Butterworth's method for shear-stress-controlled condensate flow gives reasonable agreement between simulation results and industrial data, while Chen et al.'s method can better describe the transition process of condensate flow from laminar to turbulent flow.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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