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  • Chemical Engineering  (1,326)
  • 1990-1994  (1,326)
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  • 101
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 116-127 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Singularity theory is combined with asymptotic analysis to determine the exact uniqueness-multiplicity boundary and ignition and extinction locus for the non-adiabatic, autothermal tubular reactor model. It is found that the steady-state behavior of the nonadiabatic reactor is described by the two limiting cases of adiabatic and strongly cooled models. The adiabatic case has been examined in a previous study. Here, we develop limiting models to describe the strongly cooled asymptotes. We also classify the different types of bifurcation diagrams of conversion vs. residence time using the results of singularity theory with a distinguished parameter. Analytical criteria are developed for predicting the conditions under which autothermal operation is feasible when heat losses are significant.
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  • 102
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 149-152 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 103
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 104
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 201-210 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two-and one-dimensional steady-state isothermal mathematical models of monolith reactors for selective catalytic reduction (SCR) of NOx by NH3 are compared for circular, square and triangular geometry, as well as for linear and Rideal kinetics. Solutions for the two-dimensional model demonstrate that, as the reaction rate decreases from infinity to zero, the Sherwood number varies from the values of the Nusselt number characteristic of the Graetz-Nusselt problem with constant wall temperature to those with constant wall heat flux but with peripherally varying temperature. A lumped-parameter treatment, based on similarity with the constant wall temperature heat transfer problem, agrees satisfactorily with the solutions for a far more expensive two-dimensional model. The agreement is excellent for square channels, but the NH3 slip tends to be underestimated in the triangular geometry. The one-dimensional model reproduces successfully experimental effects of the NH3/NO feed ratio, and of the area velocity and the size of monolith channels.
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  • 105
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 219-226 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Current AC (alternating current) techniques are used often to characterize the energetics at a semiconducting solid phase/electrolyte interface. For thin layers having a strongly disordered or amorphous structure (such as oxide-passive layers anodically grown on valve metals), interpretative models currently used for crystalline semiconductors may produce misleading data.A new interpretation of the admittance data, based on recent models for amorphous semiconductors (a-Sc) Schottky barriers, is presented for passive films of Nb, W and Ti. The physical bases of the model are presented as well as its advantages and disadvantages. The new theory views the solid/electrolyte interface more satisfactorily and provides information on the solid-state properties and the electronic structure of the electrode useful for interpreting the electron exchange between the solid phase and redox couples in solution.
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  • 106
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 26-40 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The design of controllers for nonlinear, nonminimum-phase processes is one of the most difficult control problems currently faced. Current available control algorithms for nonlinear processes rely implicitly or explicitly on an inverse of the process. Linear control methods for nonminimum-phase processes are based on a decomposition of the process into a minimum-phase and a nonminimum-phase part. Such a decomposition is an open problem for nonlinear systems.In this work, a control structure called the minimum-phase output predictor for nonlinear, nonminimum-phase processes is developed. The structure is based on the notion of statically equivalent outputs; a minimum-phase, statically equivalent output is estimated on-line and then an available nonlinear control algorithm is used to control it to set point. The advantage of the proposed formulation is that it is based on the calculation of an output function, not on a decomposition of the process dynamics. The proposed control methodology is applied and its performance is evaluated for a chemical engineering example.
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  • 107
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 67-75 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Clarke et al. (1986) have developed a model-based verification method and have applied it to validation of VLSI circuits. We have used the method to test automatically the safety and operability of discrete chemical process control systems. The technique involves: (1) a “system model” describing the process and its software; (2) “assertions” in temporal logic expressing user-supplied questions about the system behavior with respect to safety and operability; and (3) a “model checker” that determines if the system model satisfies each of the assertions and provides a counterexample to locate the error if one exists. Temporal logic is used for reasoning about occurrence of events over time. To reveal discrete event errors, we have applied the verification method to a simple combustion system and an alarm acknowledge system.
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  • 108
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 93-100 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: One of the major obstacles to overcome for the realization of economical hydrogen-oxygen, polymer-electrolyte fuel cells is the high capital cost of the inert perfluorosulfonic acid (PSA) membranes, which provide a pathway for ionic transport between the cell electrodes. It has recently been shown that composite polymer membranes can be synthesized by depositing PSA polymers onto porous poly(tetrafluoroethyene) (PTFE) substrates. The resulting membranes are mechanically durable and quite thin relative to traditional PSA membranes; we expect the composite membranes to be of low resistance and cost. In this experimental study, we examine the composite membrane properties as a function of the membrane composition. Our results allow us to form a conceptual model to explain both the equilibrium and transport characteristics of these materials. For high PSA contents, the membrane behavior is similar to that of the PSA polymer; the water permeability, however, is reduced significantly. For intermediate PSA contents, the membranes have a high porosity and match the thickness of the PTFE substrate (≈50 μm); membranes of this composition range are potentially useful candidates for fuel cells because of their high resistance to water transport and reduced ionic resistance. Composite membranes of very low PSA content demonstrate characteristics similar to the hydrophobic PTFE substrate and are not of interest for fuel cells.
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  • 109
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    AIChE Journal 38 (1992), S. 479-479 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 110
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    AIChE Journal 38 (1992), S. 489-501 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The coupled, unsteady Navier-Stokes, convective diffusion, and thermal energy equations that describe spin coating of colloidal suspensions are solved numerically. The theoretical model, absent of any adjustable parameters, is used to explore the effects of angular velocity, initial solvent weight fraction, solvent properties and spin coating protocol on the evolution of temperature and concentration profiles in the liquid film during spin coating. The predicted coated film thickness is found to be in excellent quantitative agreement with spin coating experiments performed with both hard-sphere and nonhard-sphere suspensions of monodisperse latex particles in water. The coated film thickness, determined by ellipsometry, is shown to depend on the inverse square root of the angular velocity except at high ionic strength when the dependence on angular velocity is weaker. Timescales that characterize spin coating of colloidal suspensions are shown to be quite different from those that characterize spin coating of polymer solutions, and consequently simple models for predicting the coated film thickness of polymer solutions (Bornside et al., 1991; Lawrence, 1989) are shown to be inadequate for colloidal suspensions. Rapid substrate acceleration, high rotation rates, partial saturation of the overlying gas phase, and high initial solids concentration are identified as spin coating protocols that suppress a convective instability that produces radial striations in the coated film.
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  • 111
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 535-543 
    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 hybrid model is developed and implemented for predicting the limiting bound of the reactant conversion rate in an isotropic turbulent flow under the influence of a reaction of the type A + B Products. This model is based on the amplitude mapping closure of Kraichnan for the molecular mixing of a stochastically distributed scalar, and the eddy-damped quasi-normal Markovian (EDQNM) spectral closure for the two-point scalar covariance. The results predicted by this model compare well with available experimental data in both gaseous and aqueous plug-flow reactors, but point to the need for more detailed measurements in future experimental studies. With the implementation of the mapping closure, a simple analytical expression is obtained for the decay rate of the unmixedness. This expression is very convenient and is recommended for direct practical applications in the modeling and design of plug-flow reactors.
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  • 112
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    AIChE Journal 38 (1992), S. 237-243 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental study has been carried out of the in situ thermal degradation of a commercial dehydrogenation catalyst in a fixed-bed reactor. The activity of catalyst particles sampled at different reactor positions after several reaction-regeneration cycles has been related to their time-temperature history, according to the following kinetics: \documentclass{article}\pagestyle{empty}\begin{document}$$ - da_0 /dt = 0.147{\rm exp}(- 73,600/RT)a_0^{2.2} $$\end{document}The above equation represents the loss of activity under coke-free conditions, that is, activity loss due to sintering. The results of the study show that important differences in catalytic activity can be obtained for different positions of a fixed-bed catalytic reactor after several operation-regeneration cycles.
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  • 113
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    AIChE Journal 38 (1992), S. 259-272 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The diffusion of proteins in polymer matrices is an important step in the adsorptive and chromatographic processes used for protein purification, as it is often rate-limiting. Methods for the estimation of the intraparticle diffusivity in polymer gels have been developed and were applied to the diffusion of seven model proteins in agarose particles. The intraparticle diffusivity was not affected by particle diameter. A correlation based on the restricted diffusion model of Ogston et al. (1973) and Cukier (1984) has been proposed. This correlation allows the estimation of protein diffusivity in these matrices based on the molecular weight of the protein and the polymer concentration.
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  • 114
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 291-296 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The concept of optimal catalyst activity distribution is studied experimentally for the ethylene epoxidation reaction network on a Ag/α-Al2O3 catalyst in a single-pellet reactor. The Dirac delta-type distribution of the catalyst is approximated by a step distribution of narrow width. For a fixed amount of silver, the influence of location and width of the catalytically active layer on the conversion of ethylene and on the selectivity and yield to ethylene oxide is investigated under oxygen-rich conditions in the temperature range 210-270°C. The results clearly demonstrate that for optimum selectivity and yield to ethylene oxide, the silver catalyst should be placed in a thin layer at the external surface of the pellet.
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  • 115
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    AIChE Journal 38 (1992), S. 315-315 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 116
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    AIChE Journal 38 (1992), S. 1871-1880 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dynamic behaviour of an adiabatic tubular plant reactor during the startup is demonstrated, together with the impact of a feed-pump failure of one of the reactants. A dynamic model of the reactor system is presented, and the system response is calculated as a function of experimentally-determined, time-dependent, manipulated variables. The values of model parameters are estimated by using the SimuSolv (1991) computer program. The data set collected during the reactor start-up is used for the parameter estimation procedure. An excellent agreement is obtained between the experimental and the calculated system response. Many continuously-operated commercial reactors require a complete conversion of one of the main reactants at the reactor exit. It is shown that for an industrial tubular reactor a much higher initial reactor temperature is required during the startup, compared to the reactor inlet temperature during normal steady-state operation, to ensure a complete reactant conversion. Much more research is necessary to determine whether this is a generally valid rule.
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  • 117
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    AIChE Journal 38 (1992), S. 1913-1915 
    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 semi-empirical model of the radial segregation of solids in upward flow of dilute gas-particle suspensions in riser systems is presented on the basis of a reduced form of the fundamental two-phase flow governing equations and experimental evidence concerning the solids concentration at the wall. The following simple expression for the radial solids concentration profile is obtained: \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{1 - {\rm \varepsilon }}}{{{\rm 1} - {\rm \varepsilon }}} = 2\left( {\frac{r}{R}} \right)^2 $$\end{document} and is in agreement with experimental data over a wide range of operating conditions: superficial gas velocity from 1.4 to 15.3 m/s, riser diameter from 0.032 to 0.40 m, imposed solids flux from 6.60 to 207 kg/m2·s, mean particle size from 32 to 120 μm and particle density from 1,000 to 3,500 kg/m3.The model confirms the existence of the core-annulus flow structure in gas-particle suspensions reported in riser reactors, circulating fluidized beds, and the freeboard of bubbling fluidized beds.
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  • 118
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    AIChE Journal 38 (1992), S. 835-846 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Batch, fed-batch, and single-stage CSTR bioreactors operate without external sources of biomass after they have been inoculated. However, other kinds of bioreactors, such as the second and subsequent reactors in a cascade of CSTRs, operate with continuous introduction of biomass from one or more external sources. The biomass in a bioreactor with an external source is not homogeneous with respect to past history of environmental conditions, and growth of this biomass is not balanced (steady-state) growth even when the bioreactor operates in steady state. So-called unstructured models of growth, which assume biomass to lack any internal structure or to have an invariant internal state, can give only a first approximation to the growth rate behavior of the biomass in a bioreactor with an external source of biomass. Structured models, which endow biomass with a changeable internal structure, are required to obtain more accurate predictions of growth rate behavior in such reactors. Introduction of structure is not sufficient for improved accuracy, however, and the fact that biomasses from different sources are remain segregated from one another must also be accounted for by any structured growth model used. This article presents, among others, the systems of different equations that result from application of the notions to the reactors of a cascade of CSTRs.
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  • 119
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    AIChE Journal 38 (1992), S. 1309-1328 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: We examine the simplest homogeneous azeotropic distillation sequence of industrial relevance, where an entrainer is added to a binary azeotrope to recover both azeotropic constituents as pure products. Despite its apparent simplicity, such distillation columns can exhibit an unusual behavior not observed in zeotropic distillation: For some mixtures, separation as a function of reflux goes through a maximum. At infinite reflux, no separation is achieved.In some cases, achieving the same specifications with a larger number of trays requires a larger reflux.Sometimes the only feasible separation yields the intermediate component as a pure distillate, while the bottom product contains the light and heavy components.Sometimes the only feasible separation yields the intermediate component as a pure bottom product while the distillate contains the light and heavy components.While these unusual features can be regarded as curiosities, they are essential for proper entrainer selection and design. For a minimum boiling azeotrope, the existing and conflicting entrainer selection rules state that one should use a component that introduces no distillation boundary between the azeotropic constituents (Doherty and Caldarola, 1985), and either a low or high boiling component that introduces no additional azeotrope or a component which introduces new minimum boiling azeotropes (Stichlmair et al., 1989). By taking advantage of the curious aforementioned features, as well as our experience involving more than 400 mixtures, we have been able to analyze the assumptions behind these criteria, show when those assumptions break down, and therefore understand the limitations of the criteria.
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  • 120
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    AIChE Journal 38 (1992), S. 1161-1169 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The overlapping grain model was used to describe the sulfidation of zinc oxide and zinc-titanium oxide powders at temperatures between 400-700°C in H2S-H2-N2 gas mixtures. Experimental data were collected under conditions free of mass-transfer and pore diffusion limitations. Thus, the only resistances to reaction were due to intrinsic sulfidation kinetics (surface reaction) and diffusion through the product layer. The product layer diffusion coefficient was used as a fitting parameter in the model. As the relative amount of titanium in the sorbent was increased, the product layer diffusion coefficient decreased. Similar activation energies (26.6 kcal/mol) were obtained for the product layer diffusion coefficient of ZnO and Zn-Ti-O sulfidation. From the similarity in activation energies, it is proposed that for both types of sorbents diffusion occurs primarily through ZnS.
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  • 121
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    AIChE Journal 39 (1993), S. 422-433 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The memory integral based on convolution of the unit step response to loading a clean pellet with concentration history at the pellet surface is proposed for computations of mass transfer in adsorption process simulation. Although rate laws are widely used to describe diffusion and sorption in pellets for slow (Glueckauf, 1955) and moderate (Kim, 1989) rates of mass transfer, these models fail to describe mass transfer at short contact times because the concentration history experienced by the pellet is not accounted for. To facilitate memory integral computations, approximations to the unit step response to loading a clean pellet are derived based on a single moving finite element and by asymptotic matching in time. Numerical evaluation of the memory integral is demonstrated on simple cycles which show the merits of this approach.
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  • 122
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    AIChE Journal 38 (1992), S. 1243-1253 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The degree of hydrogen bonding and macroscopic thermodynamic properties for pure and mixed fluids are predicted with the hydrogen bonding lattice fluid (LFHB) equation of state over a wide range in density encompassing the gas, liquid and supercritical states. The model is successful for molecules forming complex self-associated networks, in this case pure methanol, ethanol, and water, and the mixture 1-hexanol-SF6. In supercritical water, significant hydrogen bonding is still present despite all the thermal energy and is highly pressure- and temperature-dependent. A fundamental description of pressure and temperature effects on hydrogen bonding is presented for a well-defined case, the formation of a complex between a donor and acceptor in an inert solvent, where no self-association is present. The partial molar enthalpy and volume change on complexation both become pronounced near the critical point, where the density is highly variable with temperature and pressure.
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  • 123
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    AIChE Journal 39 (1993), S. 397-412 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The problem of bulk, transition and Knudsen regime diffusion in structures of freely overlapping fibers of various orientation distributions was numerically investigated, and the interrelation of the resulting effective diffusivities was examined. Fibers were randomly positioned and oriented in d = 1, 2, or 3 directions. A Monte Carlo simulation scheme was employed to determine the effective diffusivities from the mean-square displacement of random walkers traveling in the interior of the porous structure. The effective diffusivity was found to depend strongly on the orientational distribution of the fibers, porosity of the fibrous structures, and Knudsen number. The tortuosity factor decreased in general with increasing porosity, approaching at the limit of dilute beds the lower bound derived for each direction of diffusion from variational principles. The simulation results agreed well with experimental values of the bulk tortuosity of fibrous beds from the literature. It was also found that the reciprocal additivity or harmonic average effective diffusivity expression (Bosanquet formula), commonly used to estimate transition regime diffusivities from the values at the ordinary and Knudsen diffusion limits, provides an excellent approximation for the effective diffusivity of fibrous beds, except for that parallel to the fibers of a unidirectional structure.
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  • 124
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    AIChE Journal 39 (1993), S. 461-470 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The asymptotic behavior of fixed-point methods in the complex domain is studied. Both direct substitution and Newton's method exhibit stable periodic and aperiodic behavior from real- or complex-valued starting points. Moreover, multiple stable periodic orbits can exist for direct substitution. Traditional trust region (or dogleg) methods, on the other hand, often terminate at singular points, which correspond to nonzero-valued saddlepoints in the least-squares function that can be arbitrarily far from a solution. Furthermore, the basins of attraction of these singular points are usually dispersed throughout the basin boundaries in the complex domain, clearly illustrating that singular points (via the dogleg strategy) also attract either real- or complex-valued starting points.In light of this, an extension of the dogleg strategy to the complex domain, based on a simple norm-reducing, singular point perturbation, is proposed. This extended trust region method removes all forms of nonconvergent behavior and always terminates at a fixed point, even from critical point (worst-case) initial values. Many numerical results and geometric illustrations using chemical process simulation examples are presented.
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  • 125
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    AIChE Journal 39 (1993), S. 446-460 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Most of the advanced nonlinear control algorithms require a model of the system to be controlled. Unfortunately, most of the processes in the chemical industry are nonlinear, and fundamental models describing them are lacking. Thus there is a need for the identification and control of nonlinear systems through available inputoutput data. In this article, we briefly introduce the input-output model used (polynomial ARMA models), and analyze its stability and invertibility. This paves the way to the development of a nonlinear-model-predictive controller. Implementation issues such as modeling of disturbance, state and parameter estimation are discussed. The theory presented is illustrated through examples.
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  • 126
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    AIChE Journal 39 (1993), S. 471-492 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The separation of a binary mixture, using a third component having intermediate adsorptivity as desorbent, in a four section countercurrent adsorption separation unit is considered. A procedure for the optimal and robust design of the unit is developed in the frame of Equilibrium Theory, using a model where the adsorption equilibria are described through the constant selectivity stoichiometric model, while mass-transfer resistances and axial mixing are neglected.By requiring that the unit achieves complete separation, it is possible to identify a set of implicit constraints on the operating parameters, that is, the flow rate ratios in the four sections of the unit. From these constraints explicit bounds on the operating parameters are obtained, thus yielding a region in the operating parameters space, which can be drawn a priori in terms of the adsorption equilibrium constants and the feed composition.This result provides a very convenient tool to determine both optimal and robust operating conditions. The latter issue is addressed by first analyzing the various possible sources of disturbances, as well as their effect on the separation performance. Next, the criteria for the robust design of the unit are discussed. Finally, these theoretical findings are compared with a set of experimental results obtained in a six port simulated moving bed adsorption separation unit operated in the vapor phase.
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    AIChE Journal 39 (1993), S. 505-509 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 513-517 
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    AIChE Journal 39 (1993), S. 518-520 
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    AIChE Journal 39 (1993), S. 510-512 
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    AIChE Journal 38 (1992), S. 1477-1480 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 38 (1992), S. 1488-1488 
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    AIChE Journal 38 (1992), S. 1493-1498 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Racemic leucine can be separated into d- and l-isomers by fractional extraction across microporous hollow fibers. In this extraction, an aqueous solution of the racemate is fed to the lumen of the fibers, and an octanol solution of dodecyl-l-hydroxyproline flows countercurrently outside of the fibers. The interface between feed and extractant is stabilized by filling the pores in the hollow-fiber walls with a cross-linked polyvinylalcohol gel which offers negligible resistance to mass transfer. The extraction with dodecyl-l-hydroxyproline deliberately imitates earlier studies, facilitating comparisons of hollow-fiber extraction with other techniques. The results show that the isomer yield per equipment volume of racemic separation is 100 times greater than that in a continuously rotating extractor, and 1,000 times greater than that in a conventional packed tower.
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    AIChE Journal 38 (1992), S. 1609-1617 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Wrong-way behavior refers to a large transient temperature increase caused by a sudden reduction in the feed temperature or increase in the feed rate to a packed-bed reactor operating at an intermediate or high level of conversion. This dynamic temperature rise may be affected by reactant adsorption on the inert catalyst support. The wrong-way behavior usually leads to formation of a downstream-moving temperature front. In such cases, reactant adsorption tends to moderate and decrease the maximal transient temperature of these fronts. However, when the wrong-way behavior generates an upstream-moving temperature front, reactant adsorption may substantially increase the temperature rise over that attained in its absence and ignite the reactor. Reactant adsorption may also lead to surprising dynamic effects upon changes in feed velocity.
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    AIChE Journal 38 (1992), S. 1631-1638 
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    Keywords: Chemistry ; Chemical Engineering
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    Notes: Diffusional transport in a network of branching conduits is considered. The branching network is idealized as an ensemble of identical branching segments. Starting with the general species continuity equation, multiscale perturbation analysis is used to derive a one-dimensional, effective transport equation for species concentration. The macrotransport equation contains an effective diffusion coefficient, D*, which arises naturally from the analysis. D* can be computed from a local diffusion problem posed on an individual branching segment of the ensemble network. The local relations defining D* bear clear similarity to their counterparts for transport in spatially periodic porous media. Although this study was originally directed toward describing gas diffusion in the peripheral airspaces of the lung, the results provide insight for other transport processes occurring in branching networks.
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    AIChE Journal 38 (1992), S. 1649-1655 
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    Notes: The study of LeVan et al. (1988) concerning the dynamics of mixed-gas adsorption of components having high concentrations is extended to the case of multicomponent isotherms determined from either ideal or nonideal adsorbed solution theory. A discussion is given of the effect of isotherm properties on the dynamics of isothermal, mixed-gas adsorption when the adsorbate concentrations in the feed gas are large enough so that the interstitial fluid velocity varies significantly along the adsorption front.
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    AIChE Journal 38 (1992), S. 1662-1666 
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    AIChE Journal 38 (1992), S. 1671-1674 
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    AIChE Journal 38 (1992), S. 1675-1682 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 38 (1992), S. 1703-1715 
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    Keywords: Chemistry ; Chemical Engineering
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    Notes: One of the limitations of today's knowledge-based (KB) systems for diagnostics and supervision is a lack of adequate temporal reasoning mechanisms. Most of these systems are designed primarily to operate with the current values of the process variables and, sometimes, with their derivatives. Such simple capabilities, however, are not always sufficient to identify some complex dynamic phenomena, which in many cases leave their own unique “stamp” on the process behavior, expressed in the form of characteristic temporal shapes of the related variables. To detect and diagnose adequately the events of interest, the KB system should be able to reason about the temporal shapes of the process variables. Although during manual supervision process operators rely heavily on such characteristic shapes as reliable symptoms of underlying phenomena, their exploitation has not been considered seriously by the designers of KB control systems. We propose a generic methodology for qualitative analysis of the temporal shapes of continuous process variables designed to be embedded into a real-time KB environment. It is applicable to bioprocesses, as well as to other complex dynamic systems.
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    AIChE Journal 38 (1992), S. 1729-1743 
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    Keywords: Chemistry ; Chemical Engineering
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    Notes: Practical guidelines are required for the design and operation of complicated catalytic packed-bed reactors. Primary among design considerations is the avoidance of operating regions of high parametric sensitivity, in which small changes in operating conditions can lead to thermal runaway in the reactor. Existing criteria for predicting these regions rely on complex mathematical formulations for differential sensitivity between input and output variables. The present work centers on the development of practical design criteria for avoiding reactor instability and temperature sensitivity in multitubular packed-bed reactors. A set of simple guidelines is proposed for the sizing of reactors and proper selection of operating conditions. The implications of these open-loop sensitivities for a controlled reactor are investigated. It is shown through simulation studies that violation of the proposed criteria leads to control problems and difficulty in operating at the design point.
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    AIChE Journal 38 (1992), S. 1751-1760 
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    Notes: The experimental validation of on-line estimation of multiple specific growth rates for the bakers' yeast fed-batch process is presented. Pole placement based parameter estimation combined with an asymptotic biomass observer constitute the basic algorithm. The full process model being ill-conditioned for estimation using the available measured state variables, the use of two partial models related to two different states of the process is suggested. An alternating procedure between two sets of estimation algorithms designed from the partial models is proposed. The performance of the alternating procedure is validated both with simulated and experimental data. The accuracy of the estimates of the three specific growth rates involved in this process is verified according to two criteria based on the respiratory quotient and on the evaluation of the ethanol production/consumption rate.
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    AIChE Journal 38 (1992), S. 1761-1768 
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    Notes: Binary diffusion coefficients of some organic compounds in carbon dioxide at 313.2 K and 16.0/25.0 MPa were measured by using the Taylor-Aris tracer response technique. We propose a new correlation of Schmidt numbers as a function of solvent molar volumes for predicting binary diffusion coefficients in dence CO2 and self-diffusion coefficients of dense CO2. The correlation was also found to be valid for predicting self-diffusion coefficients of dense CH4 at Fv/A* 〈 40 or v2/(ṽ2)0 〉 1.62.
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    AIChE Journal 38 (1992), S. 1825-1834 
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    Notes: Unsteady axial mixing due to addition of a batch of sodium chloride solution at the top of a water-filled tube (2.63 cm i.d.) has been studied by measuring the developing concentration profile and the advancing front with dye added to the brine. Data have also been obtained with added baffle plates, with the use of a viscous aqueous solution, and in smaller diameter (1.48, 1.91 cm) tubes. Results can be approximately correlated by means of a model based on unsteady one-dimensional turbulent dispersion. Laminar flow affects the behavior of the advancing front at which the salt concentration is lowest.
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    AIChE Journal 38 (1992), S. 1816-1824 
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    Notes: The problem of diffusion in pore networks that are close to a percolation threshold is considered. Such networks arise: if the network is poorly connected; if the diffusing molecules are of a comparable size to the pores so that the fraction of the network accessible to the molecules is close to the percolation threshold; and in solids with multimodal pore-size distributions in which the pores belonging to the largest mode form a network close to the percolation threshold. We have investigated diffusion in such networks, using a new method in which the mass balance equations for diffusion on a regular lattice are solved using a Monte Carlo approach, coupled with a renormalized effective medium approximation. The method is accurate both close to and far from the percolation threshold, and is fast enough for routine calculations, such as in catalyst design applications.
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    AIChE Journal 38 (1992), S. 1835-1839 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 38 (1992) 
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    AIChE Journal 38 (1992), S. 1843-1846 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1716-1720 
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    Keywords: Chemistry ; Chemical Engineering
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    Notes: Chabazite zeolites are used at Oak Ridge National Laboratory to decontaminate wastewaters containing 90Sr and 137Cs. Treatability studies show that chabazite can remove trace amounts of these nuclides from wastewaters containing much higher concentrations of calcium and magnesium. The design of ion-exchange columns for multicomponent systems requires a method for predicting multicomponent equilibria from binary, ternary and quaternary experiments, since the number of experiments required for an empirical equilibrium model is not generally feasible. Binary interaction parameters for the Wilson equation are used to predict solid-phase activity coefficients for the five-component system. The sum of squares of deviations between experimental and predicted solution concentrations for the data points available is calculated. The average deviation per data point for the five-component system is lower than for some of the ternary-and four-component data sets containing calcium or magnesium.
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    AIChE Journal 39 (1993), S. 1708-1715 
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    Notes: The limiting current technique was used to measure area-averaged mass-transfer coefficients for surfaces containing many small reactive areas arranged in various patterns. Partially masked platinum electrodes were fabricated using photolithography, and mass-transfer measurements were performed with a rotating disk apparatus. The average mass-transfer coefficient was sensitive to the fraction of the electrode area exposed (ε), declining from values near that for a fully exposed surface for ε = 0.5 to less than 1% of the fully exposed value for ε = 0.001. For any given ε, the mass-transfer coefficient declined with increased spacing between reactive sites. The results were relatively insensitive to details of the site distribution, such as whether the sites were arranged in regular arrays (square or hexagonal lattices) or distributed randomly over the surface. For all conditions studied, the mass-transfer coefficient greatly exceeded that predicted by conventional models which apply the stagnant film approximation to the fluid surrounding a representative active site. This finding is qualitatively consistent with recent computational results, which suggest that convective transport enhances mass transfer at partially active surfaces to an extent not accounted for by adjustments in the effective film thickness.
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    AIChE Journal 39 (1993), S. 1720-1720 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 38 (1992), S. 251-258 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Research has been carried out on the use of NCS (Network Computing System) to distribute the processing of a finite element application to multiple computers at once. Coarse-grained parallelism of specific routines on loosely coupled CPUs has been implemented and tested. In a step-by-step fashion, the method of using NCS to convert finite element software POLY2D is explained for its application in parallel computing resources throughout a network. For the modeling of a simple conductive heat transfer problem, the distributed version of POLY2D on a homogeneous token ring network of nine Apollo workstations is used. Some timings given are compared to those obtained from a standard nondistributed simulation.
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    AIChE Journal 38 (1992), S. 284-290 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Resistively heated filaments are used to deposit diamond or to act as a substrate in the manufacture of ceramic fibers. This article analyzes the effects of an AC power source, in particular the oscillation in filament temperature and its influence on the kinetic rates, as well as the vibration of the filament, when it is mounted in a state of tensile stress. These effects diminish when the filament gauge is large enough and the analysis can help to decide whether an AC or a DC power source should be used.
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    AIChE Journal 38 (1992), S. 311-314 
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    AIChE Journal 38 (1992), S. 328-342 
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    Notes: An experimental study of a semibatch reaction crystallization is presented. Dilute hydrochloric acid is fed to a stirred solution of sodium benzoate to crystallize benzoic acid. The weight mean size of the product crystals increases with increasing stirring rate, reaches a maximum, and then decreases again. Larger crystals may be produced if the reactant feed point is positioned close to the outlet stream of the impeller. At equal power input the influence of stirrer type is negligible. Decreasing reactant concentrations or feed rate increases the crystal size significantly. Experimental results are explained qualitatively focusing on nucleation and growth conditions and on feed point mixing. The feed point micromixing brings reactants together to generate supersaturation and allow for nucleation. Continued mixing, however, may partially dilute supersaturation before nucleation takes place or may restrict nuclei growth, thus promoting more efficient Ostwald ripening in the bulk. This may result in high bulk supersaturations which in turn hampers the dilution effects.
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    AIChE Journal 38 (1992), S. 397-404 
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    Keywords: Chemistry ; Chemical Engineering
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    Notes: A reasonable analytical procedure of the overall reaction rate for the phase transfer catalysis with mass transfer is discussed. Alkaline hydrolysis of n-butyl acetate with a phase transfer catalyst Aliquat 336 (tricaprylmethylammonium chloride, Q+Cl-) was chosen as a model system and carried out in an agitated vessel with a flat interface. Overall reaction rates observed were proportional to the interfacial concentration of the actual reactant Q+OH- (the ion pair consisting of quaternary ammonium cation Q+ and OH-) for the hydrolysis in the organic phase. The interfacial concentration of Q+OH- was a unique function of bulk concentrations of the catalyst and NaOH, and the ionic strength of the aqueous solution. This behavior of the overall reaction rates was explained by the proposed model solution. The reaction rate constant, evaluated by fitting the rate data to the model prediction, was 47 m3/kmol·s at 298 K. It was 70 or more times greater than that of conventional alkaline hydrolysis in the aqueous phase.
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    AIChE Journal 38 (1992), S. 425-437 
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    Keywords: Chemistry ; Chemical Engineering
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    Notes: Effects of mixing on number- and weight-average degree of polymerization in free radical homopolymerization in solution in a semibatch stirred tank-reactor have been modeled by use of the “partially segregated feed” model of Villermaux (1989) and the lumped kinetic treatment of addition polymerization. Mixing conditions are described in terms of the dimensionless time constants θM and θX for convective and diffusive mixing, respectively. Results show that DPn is relatively insensitive, while DPw is highly sensitive to mixing conditions. Comparison with ideal mixing results shows that polydispersity (DPw/DPn) can rise greatly as mixing becomes increasingly nonideal, depending on the value of dimensionless flow rate and dimensionless initiator rate constant. Time constants of the mixing model need to be expressed as dimensional correlations before the proposed polymerization model can be compared to experimental measurements. The model may be adapted to melt polymerization in nonideal CSTR such as LDPE.
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    AIChE Journal 39 (1993), S. 1272-1280 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An instability analysis has been carried out to elucidate the unsteady flow conditions encountered in the typical circulating fluidized bed units in light of the conveyor-solids feeder interaction. The results successfully predict the critical velocity and the maximum solids circulation rates reported in the literature and explain the origin of such unstable conditions. Furthermore, the simulation, for the first time, reveals the importance of unit structure in improving the performance of circulating fluidized bed systems. Finally, the concept of a high-density circulating fluidized bed is proposed.
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    AIChE Journal 39 (1993), S. 1303-1321 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The product compositions in single-feed distillation columns can be specified only in certain regions of the composition space, which depend only on the pressure, feed, and vapor-liquid equilibrium for the mixture. In nonideal mixtures, even without azeotropes, the regions may allow unusual product distributions. For example, the distillate in a “direct split” is composed primarily of the lightest component. Intuition and experience with relatively ideal mixtures suggest that the next most plentiful component is the intermediate boiler. In nonideal mixtures, however, with or without azeotropes, the next most plentiful component may be the highestboiling species with only trace amounts of the intermediate boiler. For azeotropic mixtures, distillation boundaries may give rise to additional restrictions on the product compositions. We describe how simple distillation boundaries deform into continuous distillation boundaries and, in a limited number of cases, how the simple distillation boundaries can be crossed in continuous columns for certain ranges of the design variables. Unfortunately, such designs may be quite sensitive to model uncertainties or to disturbances in the parameters.
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    AIChE Journal 38 (1992), S. 607-610 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 1377-1388 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Deposition of wax on the wall of oil pipelines is often regarded as a problem since the tube diameter is reduced. Consequently, more power is needed to force the same amount of oil through the system. A mathematical model for quantitative prediction of wax deposition for each hydrocarbon component has been developed. Each component is characterized by weight fraction, heat of fusion, and melting point temperature. A model explains how a phase transition in the flow from liquid oil to waxy crystals may create a local density gradient and mass flux, which depends on the local temperature gradient. The model predicts that wax deposition can be considerably reduced even when the wall temperature is below the wax appearance point, provided the liquid/solid phase transition, expressed by the change in moles of liquid with temperature, is small at the wall temperature. Deposition as function of time has been obtained as a solution of differential equations derived from the principles of mass and energy conservation and the laws of diffusion.
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    AIChE Journal 38 (1992), S. 793-796 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 1411-1414 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 1415-1419 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 1389-1397 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Rigorous and approximate methods are compared for the simulation of CO2 absorption into aqueous alkanolamine mixtures of methyldiethanolamine and diethanolamine. In addition, data for the mixtures containing monoethanolamine and the simultaneous absorption of CO2 and H2S are presented. For the rigorous approach, the simplified eddy diffusivity theory is used to simulate the liquid-phase hydrodynamic characteristics. The approximation methods examined are the pseudo-first-order approximation, the interpolation approximation of Wellek et al. (1978), the algebraic combined flux (ACFLUX) approximation and the modified combined flux (MCFLUX) approximation. The latter approximation utilizes the reaction zone concept to determine the kinetic preference of the absorbing gas at the gas-liquid interface. Under the range of conditions studied, the MCFLUX approximation predicts very accurately the CO2 and H2S flux rates in mixed amine systems, as compared with the rigorous solution of the differential equations.
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    AIChE Journal 39 (1993), S. 1406-1410 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 1420-1420 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993) 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1431-1443 
    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 steady-state method recently proposed for measuring two-phase flow properties of a porous medium is supplemented by NMR imaging for measuring the saturation gradients which are allowed to persist in the specimen. The method relies on a strong capillary end effect which is assumed to be enforced by an outlet capillary pressure boundary condition, but direct verification of this has not hitherto been available. For constant flow rates, incremented stepwise, steady-state profiles of hydrocarbon saturation So are obtained which agree with predictions that they be monotonic, nonintersecting, and convex.Using D2O for the aqueous phase allows unambiguous detection of hydrocarbon by NMR, and imaging measurements of transverse relaxation time T2 were included in the protocol. T2 shows a dependence on So which is mild but not negligible for quantitative NMR imaging.
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    AIChE Journal 39 (1993), S. 935-945 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experiment has been made on ribbing induced on a film coated over a roll surface by a two-roll system: one roll rotated with a speed and the other fixed or rotated with relatively different speeds. The two rolls have the same diameters and are placed parallel with each other by keeping a gap. Test fluids are Newtonian (glycerin/water) and viscoelastic [polyacrylamide (Separan AP30)/glycerin/water] solutions. Wavelength and depth of ribbing are measured by a newly developed technique utilizing an image of a straight bar placed above the roll and reflected on the ribbing film surface. Nondimensionalized wavelength is correlated with capillary number for Newtonian liquids, but higher for dilute Separan solutions and lower for nondilute Separan solutions than for Newtonian liquids. The depth of ribbing increases for dilute Separan solutions with nearly the same value for nondilute Separan solutions as those for Newtonian liquid. This behavior observed for the ribbing seems to have some relation to the existence of a line of vortices that occurs visibly for nondilute Separan solutions in the entrance region of the gap between the rolls. Increase in the ratio of the velocities of two rolls has an effect of increasing both the wavelength and depth of ribbing for glycerine and nondilute Separan solutions, but it has the effect of decreasing them for dilute Separan solutions. Addition of Separan in glycerine solution promotes the generation of ribbing.A string spanned near over the gap to touch the surface of the liquid pool between the gap has the effect of eliminating the ribbing. This is successful in various combinations between the speeds of the two rolls and the diameters of the string.
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    AIChE Journal 39 (1993), S. 954-961 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Variations of perturbation chromatography were used to measure Henry's constants and equilibrium isotherms of various gases on silicalite. Three different adsorbent samples were analyzed (commercial powder and extruded pellets, and laboratory-synthesized crystals), and no discernable differences among the measured parameters were noted. Henry's constants for the linear alkanes were determined from isobaric and nonisobaric chromatography experiments. They were correlated successfully with temperature and the number of carbon atoms per adsorbate molecule. Isotherms were measured from concentration pulse or tracer/concentration pulse chromatography techniques. The Flory-Huggins version of the vacancy solution model was used to correlate pure gas isotherms and predict binary behavior successfully.
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    AIChE Journal 39 (1993), S. 962-974 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Micropore diffusion coefficients for infinitely-dilute methane, ethane, propane, n-butane, and isobutane in silicalite were measured via concentration-pulse chromatography. Two different samples of large laboratory-synthesized crystals were investigated. Analysis of van Deemter plots clearly indicated the presence of a significant micropore mass-transfer resistance for isobutane. Diffusion coefficients evaluated from these plots were consistent with results measured by the membrane technique. The linear alkane data differed completely in that the micropore masstransfer resistance for these adsorbates was very small, implying that the true diffusion coefficients were too large to be measured with this system. Thus, effective diffusion coefficients evaluated from these data represent a lower limit of the true values. Comparison of this limit with nuclear magnetic resonance data was favorable, since the latter are significantly larger in magnitude. Inconsistency was observed with diffusion coefficients obtained from other macroscopic techniques including the membrane method, zero-length and tracer-pulse chromatography, and some frequency response experiments.
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    AIChE Journal 39 (1993), S. 855-866 
    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 nonlinear model-based scheme is developed for product property control in industrial gas-phase polyethylene reactors. The controller regulates instantaneous melt index and density, and provides servocontrol during grade changeovers. Hydrogen and butene feed rates are manipulated to force the product properties onto desired trajectories. During grade changeovers, these trajectories are determined from off-line dynamic optimization studies. Optimal open-loop policies for reactor temperature, bleed stream flow, catalyst feed rate, and bed level are implemented as part of the changeover strategy.The nonlinear feedback controller design is based on global input/output linearization methods. Disturbances are estimated, and plant/model mismatch is removed using an extended Kalman filter. Simulations on a complex mechanistic model of the process reveal that the nonlinear controller performs well for both regulatory and servocontrol. An analogous linear IMC controller is inadequate for disturbance rejection at different operating conditions and for control during grade changeovers. The simplicity of the nonlinear control algorithm makes it an interesting candidate for industrial application. This single controller can be used to control the properties of many grades of polyethylene made in the reactor and to accomplish near optimal changeovers between these grades.
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    AIChE Journal 39 (1993), S. 885-893 
    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 simple fluid dynamic model is developed which predicts the thinning rate of a viscous film of liquid, in contact with the smooth interior surface of a long cylindrical tube, due to the shearing action of a turbulent flow of an immiscible fluid through the tube. Experiments indicate the degree to which the model provides an accurate means of predicting viscous film removal from the tube. Similar experiments performed with electrochemically roughened tubes elucidate the limitation of this cleaning process due to surface roughness. The observed limitation is consistent with an analysis based on numerical solutions of the equations for shear flow over a rough surface.
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    AIChE Journal 39 (1993), S. 867-875 
    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 continuous electrochemically modulated complexation (EMC) process was devised to extract and concentrate a class of heterocyclic nitrogen compounds. This design is composed of flow-through electrolysis cells for redox modulation and cycling of the complexing agent and hollow-fiber membrane modules for phase contacting. The extent of both extraction and concentration was found to depend mainly on the magnitude of the distribution coefficients for both steps. Experimental results and modeling of this continuous EMC process are reported, as well as potential applications for this process for other separations.
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    AIChE Journal 39 (1993), S. 1791-1798 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Adsorption rates and thermodynamic parameters were determined for the gasphase adsorption of n-alkanes and benzene derivatives on octadecylsilyl-silica gel (ODS) by chromatographic measurement and moment analysis. Thermodynamic characteristics of adsorption phenomena on ODS were similar to those on the surface. The contribution of intraparticle diffusion to mass-transport resistance was dominant in the ODS column, and the role of surface diffusion was significant for the intraparticle diffusion. The values of the surface diffusion coefficient were of the order of 10-5 cm2/s and could be estimated by assuming that the surface migration on ODS is a tracer diffusion of an adsorbate molecule in n-octadecane.
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    AIChE Journal 39 (1993), S. 1799-1809 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nonisothermal adsorption is studied by incorporating its mathematical description into a model consisting of the full two-dimensional Navier-Stokes equations and energy and species concentration equations to simulate the processes in fixed-bed industrial adsorbers/regenerators. The model partial-differential equations are solved numerically by using well-established computational fluid dynamics techniques. The equilibrium between gas and solid is considered nonlinear, which is described by Freundlich-type equations. The transport and adsorption of a compound from a solvent to and into an adsorbent are described by a two-step process: transport through the “film” to the outer surface of the particle and diffusion into the porous particle. The effect of fill resistance is discussed, as well as a two-equation turbulence model. Solutions obtained for a typical industrial adsorber/regenerator demonstrate the potential of this method. The computed results for various flow ratios and parameters in the Freundlich equations are shown to be physically plausible.
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    AIChE Journal 39 (1993), S. 1164-1177 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The direct oxidation of CH4 to H2 and CO in O2 and in air at high temperatures over alumina foam monoliths coated with high loadings of Pt and Rh has been simulated using a 19-elementary-step model of adsorption, desorption and surface reaction steps with reaction parameters from the literature or from fits to previous experiments. The surface reaction model for Pt is in good agreement with previously reported low-pressure(0.1 to 1 torr) reactor measurements of CH4 oxidation rates at temperatures from 600 to 1,500 K and of OH radical desorption during CH4 oxidation at 1,300 to 1,600 K over polycrystalline Pt foils. The model predictions for both catalysts are also consistent with product selectivities observed over monolithic catalysts in an atmospheric-pressure laboratory-scale reactor, and the differences between Pt and Rh can be explained by comparing individual reaction steps on these surfaces. Because of the good agreement between the model and both low-and atmospheric-pressure reactor simulations, a complete energy diagram for methane oxidation at low coverages is proposed. The model results show that under CH4rich conditions at high temperatures, H2 and CO are primary products of the direct oxidation of methane via a pyrolysis mechanism.
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    AIChE Journal 39 (1993), S. 1196-1209 
    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 model for a pilot-scale chemical vapor infiltration (CVI) reactor in which multiple substrates are densified simultaneously by carbon deposition from a pyrolyzing hydrocarbon is presented. Kinetic expressions and parameters and transport properties for carbon deposition from propylene determined from experimental studies and a single substrate CVI model are incorporated into the pilot reactor model. The two-dimensional transport equations for heat, mass and momentum transfer are solved for the entire reactor to simulate the effects of varied operating conditions on substrate densification throughout the reactor during the CVI process. Of the conditions simulated, the reactor temperature was found to have the most significant impact on both the uniformity of densification and the process time required. As the temperature increased, the uniformity of densification decreased and the time at which pore blockage at the outer surface occurred was shortened. Increasing the hydrocarbon feed concentration shortened the process time, but did not affect the final level of densification, while the feed rate only affected CVI at intermediate times. Comparison between experimental pilot reactor results and model predictions were satisfactory at short and long times, but agreement was less satisfactory at intermediate times.
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    AIChE Journal 39 (1993), S. 1186-1195 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Solid-state film ion exchange (Ag+-Na+) in glass substrates has been investigated for the fabrication of passive, integrated, optical waveguides. A new ion exchange mechanism is proposed which couples the oxidation of silver metal to silver oxide and the diffusion of silver ions into the glass substrate. At high electric fields and/or high temperatures, the growth rate of a silver oxide film limits the formation of mobile silver ions and constrains the diffusion of silver into the glass. This new mechanism is able to predict the dopant distribution profile under those conditions and under conditions where a constant surface concentration is appropriate (infinitely thick oxide film). It also explains the characteristics of the current vs. time curve measured during the ion exchange process. The formation and growth of the silver oxide film were confirmed by X-ray photoelectron spectroscopy and X-ray diffraction analysis.
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    AIChE Journal 39 (1993) 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1281-1291 
    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 mechanistic model of slug flow based on a set of mass and momentum conservation equations and a number of empirical closure relations is presented. It is then shown that a simplified version of the model, which physically corresponds to the flow of long liquid slugs(long slug model, LSM), can be immediately derived from the general model. The LSM is much simpler than the general model; at the same time, the predictions obtained in the two cases are very similar, when the comparison is limited to the computation of the pressure gradient and the mean liquid holdup. The LSM successfully correlates a large set of experimental measurements relative to three pipe diameters(18, 50 and 90 mm), four inclinations (0°, ±3°, 0.3°), and two pipe lengths(17 and 34 m).
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    AIChE Journal 39 (1993), S. 1322-1329 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: We present a theoretical study of the adsorption kinetics of particles with a continuous distribution of sizes. If the particles interact with short-ranged forces, the diminishing rate of adsorption with increasing surface coverage can be attributed to a geometrical blocking effect of the preadsorbed particles. We exploit the fact that at low coverages the blocking effects result from isolated adsorbed particles to develop an analytic description of the adsorption kinetics using a moment expansion approach. We evaluate the time-dependent surface coverage, density and the average size of the adsorbed particles and compare these quantities with those of the bulk phase. The effect of desorption is studied by introducing a size-independent desorption constant, and the corresponding adsorption equilibria properties, which are valid at low coverages, are derived. Simulation results for irreversible adsorption are obtained and compared with the theoretical predictions.
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    AIChE Journal 39 (1993), S. 1938-1953 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Control structure (strategy) selection consists of the selection and pairing of manipulated and measured variables. This article outlines a procedure that uses such tools as the existence of right half plane (RHP) transmission zeros, the relative gain array, the performance relative gain array, and the closed-loop disturbance gain. The regulatory control system for the fluid catalytic cracking process is used as an example. Several authors found the Kurihara control structure to be preferable to the conventional control structure. The reason is that RHP transmission zeros limit the achievable bandwidth for the conventional control structure. Two other control structures, however, have better controllability characteristics than both the conventional and the Kurihara control structures. The sensitivity of the measurement selection and variable pairing with respect to changes in the operating point and parametric uncertainty is examined, as well as the general objectives of the regulatory control level and its interaction with the higher levels in the control hierarchy.
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    AIChE Journal 39 (1993), S. 1954-1965 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Sufficient conditions for robust closed-loop stability of a class of dynamic matrix control (DMC) systems are presented. The l1-norm is used in the objective function of the on-line optimization, thus resulting in a linear programming problem. The ideas of this work, however, are expandable to other DMC-type controllers. The keys to the stability conditions are: to use an end-condition in the moving horizon on-line optimization; to have coefficients of the move suppression term in the objective function of the on-line optimization satisfy certain inequalities; and to express the uncertainty as deviations in the unit pulse response coefficients of the nominal plant. These deviations and disturbances must also satisfy certain inequalities.An off-line tuning procedure for robust stability and performance of a class of DMC controllers is also included, which determines an optimal moving horizon length and optimal values for coefficients of the move suppression term. The applicability of our approach is elucidated through numerical simulations.
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    AIChE Journal 39 (1993), S. 1976-1984 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: We report experimental data showing the effect of temperature on polymer partitioning in the dextran (DEX500)-polyethylene glycol (PEG8000)-water system. Increasing temperature increases the concentration of PEG in the top phase and decreases the concentration of DEX in the bottom phase. A solution thermodynamic model based on local compositions with temperature-dependent parameters correlates the experimental data well, and an efficient Gibbs-free energy minimization algorithm for phase equilibrium calculations is described. The partial molar enthalpies and entropies of each of the solutes, calculated with the model, are negative and decrease in magnitude as temperature increases.
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    AIChE Journal 39 (1993), S. 1966-1975 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two cationic, copper metal complexes with different ligands were synthesized: ethylenediamine (en) [Cu(C2N8N2) (ClO4)2] and diethanolamine (Deta) {[Cu-C8H21N2O4]ClO4}. These complexes were mounted on Cab-O-Sil using nonaqueous impregnation techniques, and the loadings were determined at which multilayers formed. These samples were analyzed for copper, carbon, nitrogen and hydrogen content to determine if ligand dissociation occurred during the impregnation. Samples were decomposed in a thermal gravimetric apparatus to determine the kinetics of the thermolysis reaction in air, and the evolved gases were analyzed by gas chromatograph-mass spectrometry to determine the products of the thermolysis reaction. The results of these and earlier studies are summarized in a model that describes the effects of molecular structure upon complex-support interactions. Complexes with the ability to form hydrogen bond interactions between the ligand and the support form strong interactions with the surface of silica, whereas complexes without such hydrogen bond interactions are only weakly attracted to the silica surface. Strong interactions with the surface may also arise as a result of ligand dissociation and direct interaction of the metal ion with the surface oxygens. The charge on the complex and its shape play less important roles in determining the affinity of the metal complex with the silica.
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    AIChE Journal 38 (1992), S. 480-480 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 38 (1992), S. 511-520 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Aqueous solutions of alkanolamines are commonly used to strip acid gases (CO2 H2S) from hydrocarbon streams. Processes for stripping acid gases from gaseous streams are well understood; however, the application to liquids is not as advanced. Experimental data available are scarce for systems containing aqueous amine solutions and the constituents of liquefied petroleum gases. To this end, new data are presented for the equilibria in the system propane-water-methyldiethanolamine (MDEA). A knowledge of the phase behavior in this system is required to model the equilibria encountered in the more complex systems of industrial importance.This work is a comprehensive study of the phase equilibria in the system propane-3 M MDEA, including vapor-liquid, liquid-liquid, and vapor-liquid-liquid equilibria. Experimental measurements were made for temperatures between 0 and 150°C and pressures up to 20 MPa. The data were correlated using the Stryjek-Vera modification of the Peng-Robinson equation of state. In addition, a composition-dependent mixing rule was required to fit the data adequately.
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 555-562 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To cope with modeling uncertainties and randomness of external disturbances, a new tracking control called the natural control concept is designed. Its implementation is completely independent of the internal dynamics of a controlled system, its desired output and external disturbances. The design algorithm established ensures a prespecified exponential quality of output tracking. The theory presented in this article is applied effectively to the design of natural tracking control for a chemical reaction process described by the fourth-order, linear, state-space mathematical model.
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  • 192
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    AIChE Journal 38 (1992), S. 592-602 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The nonequilibrium tray model proposed by Young and Stewart (1990) is used to correlate published fractionation data from sieve tray columns 0.45 m to 1.2 m in diameter. The model contains a dimensionless coefficient a00 to describe the interphase heat and mass transfer, and a Peclet number Pe to describe the lateral mixing of the liquid on the tray. The coefficient a00 is investigated as a function of tray geometry and hydrodynamic variables, using an error-in-variables extension of a multiresponse parameter estimation algorithm. Data from several sources are well correlated by a simple dimensionless relation for a00, with Pe predicted from the results of Bennett and associates (1983, 1991).
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  • 193
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    AIChE Journal 38 (1992), S. 629-634 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 194
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    AIChE Journal 38 (1992), S. 651-659 
    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 this paper, a program of analysis is carried out for control of a nonlinear stirred tank reactor. By examining the uniqueness and stability properties of the reactor, the zero dynamics are analyzed. Subsequently, a model reference adaptive controller (MRAC) which explicitly takes into account the nonlinearities of the system is designed; the MRAC successfully compensates for parametric uncertainty. It is shown that even when almost all reactor parameters are unknown, global convergence over the entire phase space is achieved.
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  • 195
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    AIChE Journal 38 (1992), S. 703-715 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Influence of the tube and particle diameter and shape, as well as their ratio, on the radial heat transport in packed beds has been studied. Heat transport experiments were performed with four different packings in three wall-cooled tubes, which differed in inner diameter only. Experimental values for the effective radial heat conductivity and wall heat-transfer coefficient for the pseudo-homogeneous two-dimensional model and the overall heat-transfer coefficient for the one-dimensional model are presented. Values were obtained for glass spheres, alumina cylinders, and alumina Raschig rings. The effective radial heat conductivity and wall heat-transfer coefficient can both be correlated as a linear function of the gas flow rate. The Bodenstein number for heat at fully developed turbulent flow is influenced strongly by the shape of the packing: 10.9 for glass spheres, 7.6 for alumina cylinders, and 4.2 for alumina Raschig rings. For the same packing, no significant influence is found of the tube diameter on the effective radial heat conductivity or on the wall heat-transfer coefficient. The overall heat-transfer coefficient can be described very well by the so-called “lump equation,” which gives the relations among the overall heat-transfer coefficient, effective radial heat conductivity, and wall heat-transfer coefficient. The “lump factor,” as used in the lump equation, has a best-fit experimental value of 7.4.
    Additional Material: 9 Ill.
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  • 196
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    AIChE Journal 38 (1992), S. 716-722 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effect of particle size distribution (PSD) on the performance of a fluidized bed reactor was investigated in different hydrodynamic regimes: bubbling, slugging, turbulent and fast fluidization, with three particle size distributions, all with the same mean diameter and nearly the same particle density and BET surface area. Regime transitions were examined by measuring pressure fluctuations. Void sizes tended to be smaller and the transition from bubbling or slugging to turbulent fluidization was achieved earlier for the wide distribution powder than for the narrow PSD. At gas velocities ≤ 0.2 m/s, the conversion and reactor efficiency were not affected greatly by the PSD. However, at higher gas velocities, PSD played a significant role. For particles of wide size distribution, the conversion in the turbulent and fast fluidization regimes was usually higher than in the bubbling fluidization regime at the same dimensionless rate constant, kf′. On the other hand, for particles of narrow size distribution, the dependence of conversion on the regime is small, except for the fast fluidization regime.
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  • 197
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    AIChE Journal 38 (1992), S. 723-732 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pressure relief venting of a runway reaction with gas generation is examined in terms of the overall system response and the associated venting requirement. This article presents an exact formulation as well as an approximate analytical approach. The latter is shown to be particularly useful in vent-sizing applications. Using an aqueous hydrogen peroxide decomposition example, the analytical results are demonstrated to agree well with the exact numerical results over a wide range of overpressure. In addition, the analytical result is shown to reduce to the correct limit for a pure vapor system and offers a useful vent-sizing equation for a pure-gassy system.
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  • 198
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    AIChE Journal 38 (1992), S. 761-770 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The extraction of caffeine from whole coffee beans with supercritical carbon dioxide was studied in a continuous-flow extraction apparatus. Decaffeination rates were determined as a function of CO2 flow rate, temperature and pressure by continuously monitoring the caffeine in the effluent with a flame ionization detector. Soaking the raw beans in water prior to decaffeination enhanced the rate of extraction, which increased markedly with water content. Using CO2 saturated with water also increased the rate of extraction. The rate of decaffeination increased with pressure and temperature and was influenced by both intraparticle diffusion in the water-soaked beans and external mass transfer. A mathematical model based on a linear-driving-force approximation of mass transfer and partitioning of caffeine between the water and the supercritical CO2 describes the time-dependent process. The partition coefficient for caffeine distributed between water and supercritical CO2, the only parameter determined from the dynamic extraction rate data, increases with temperature and pressure.
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  • 199
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    AIChE Journal 38 (1992), S. 811-820 
    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 framework is developed to describe kinetics and column dynamics of ad(de)sorption from bulk liquid mixtures using surface excess as the variable to quantify the extent of adsorption. It is found that the transient rate of change of surface excess with time from a multicomponent liquid mixture can be expressed in terms of a surface excess linear-driving-force model. A local-equilibrium model can be developed to describe the column dynamics of ad(de)sorption from liquid mixtures. Both self-sharpening and proportionate pattern mass-transfer zones can be formed depending on the shape of the surface-excess isotherm and the selectivity of adsorption. Analysis of column dynamics for liquid mixture adsorption can be carried out analogous to that for adsorption from gas mixtures, when a constant pattern mass-transfer zone is formed. The length of the mass-transfer zone and the composition-time column effluent profile can also be derived analytically for such a case. Experimental kinetics and column dynamics data for ad(de)sorption of ethanol-water mixtures on a large-pore activated carbon are analyzed using these models.
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  • 200
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    AIChE Journal 38 (1992), S. 857-867 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pressurization and blowdown steps in pressure swing adsorption (PSA) with binary mixtures of inert and adsorbable species are studied. Modeling involves mass balances for the bulk fluid phase and inside particles, that is, intraparticle diffusion/convection models, momentum balance equations, and linear adsorption equilibrium isotherm. The importance of intraparticle convection in PSA is assessed. Mass transfer inside pores is enhanced by intraparticle convection, which leads to a better efficiency of adsorption (pressurization) and desorption (blowdown) processes. Performance is improved by intraparticle convection and lies between diffusion and equilibrium limits, as shown in propagation profiles of the adsorbable species mole fraction in the bed and inside particles.
    Additional Material: 9 Ill.
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