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  • Chemical Engineering  (638)
  • Animals  (466)
  • 1990-1994  (1,104)
  • 1993  (1,104)
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 37-41 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experiments are reported in which the drag of single liquid droplets settling in a tall column of another lighter immiscible liquid are measured. The experimental data for the eight pairs of liquids that were tested covered a range of droplet Reynolds numbers from 10-3 to 104. Two regimes of droplet settling were encountered. In the first regime, the droplets remained spherical, and the drag agreed very well with established solid sphere drag models. In the second regime, the droplets became deformed and oscillated; the drag was found to depart suddenly from predictions of spherical models and to increase with increasing Reynolds number. Empirical models for the point of departure from spherical drag and the coefficient of drag in the unstable regime are derived.
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  • 2
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 89-98 
    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 occurrence of instabilities in chemically reacting systems, resulting in unsteady and spatially inhomogeneous reaction rates, is a widespread phenomenon. In this article, we use nonlinear signal processing techniques to extract a simple, but accurate, dynamic model from experimental data of a system with spatiotemporal variations. The approach consists of a combination of two steps. The proper orthogonal decomposition [POD or Karhunen-Loève (KL) expansion] allows us to determine active degrees of freedom (important spatial structures) of the system. Projection onto these “modes” reduces the data to a small number of time series. Processing these time series through an artificial neural network (ANN) results in a low-dimensional, nonlinear dynamic model with almost quantitative predictive capabilities.This approach is demonstrated using spatiotemporal data from CO oxidation on a Pt (110) crystal surface. In this special case, the dynamics of the two-dimensional reaction profile can be successfully described by four modes; the ANN-based model not only correctly predicts the spatiotemporal short-term behavior, but also accurately captures the long-term dynamics (the attractor). While this approach does not substitute for fundamental modeling, it provides a systematic framework for processing experimental data from a wide variety of spatiotemporally varying reaction engineering processes.
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  • 3
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 288-293 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nonlinear kinetics in multicomponent mixtures are best described in terms of continuous distribution functions. The quasilinearization procedure that we introduced in 1988 for “uniform” kinetics does not carry over to problems where second-order derivatives appear, as in all cases where diffusion phenomena are of importance. We analyze a simple diffusion-reaction problem in a porous catalyst, by making use of a perturbation technique. The general conclusions reached from this specific problem can be generalized to a wider class of diffusion-reaction problems in complex mixtures.
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  • 4
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 322-334 
    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 is developed to predict the coalescence behavior in liquid-liquid dispersions. Coalescence times are based on the lifetimes of the single films that are formed between adjoining drops in a creamed or sedimented dispersion. The model is developed for smaller drop sized dispersions (〈100 μm) in which the drops are not substantially deformed due to gravitational forces. The model predicts that coalescence occurs between the emulsion drops without the gross separation of the dispersed phase (that is, the dispersion does not separate into distinct oil and water phases). As a result of interdrop coalescence, the mean drop size of the dispersed phase increases along with an increase in the polydispersity of the drop size. The model's predictions are used to develop a quantitative relationship between the lifetime of the single film and the rate of increase of the mean drop size of the dispersion. The model also accounts for the effect on dispersion stability via the models of single film drainage in the presence of surfactant.
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  • 5
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 224-234 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Liquid circulation and a finite entrance zone are accounted for in modeling gas absorption into cocurrent flows of pure oxygen and CMC solutions. The new models lead to a Taylor-like correction factor to account for circulation in both absorption and transient dispersion experiments. Steady-state experiments for viscosities of 1, 12, 25 and 50 mPa·s were conducted by measuring dissolved gas concentration profiles along the column axis. Liquid mixing experiments were performed using the transient acid-base neutralization method, leading to measured values of axial dispersion coefficients which depended on viscosity to the power 0.75. Measurements suggest that circulation was minuscule owing to uniform gas injection by Flexisparger in the present column.
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  • 6
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 262-287 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This article discusses the existing linear model predictive control concepts in a unified theoretical framework based on a stabilizing, infinite horizon, linear quadratic regulator. In order to represent unstable as well as stable multivariable systems, the standard state-space formulation is used for the plant model. The incorporation of a nominally stabilizing constrained regulator eliminates the current requirement of tuning for nominal stability. Output feedback is addressed in the well-established framework of the linear quadratic state-estimation problem. This framework allows the flexibility to handle nonsquare systems, noisy inputs and outputs, and nonzero input, output, and state disturbances. This formulation subsumes the integral control schemes designed to remove steady-state offset currently in industrial use. The online implementation of the controller requires the solution of a standard quadratic program that is no more computationally intensive than existing algorithms.
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  • 7
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 335-343 
    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 new equation of state for electrolyte solutions has been developed from an expression of the Helmholtz free energy containing a nonelectrolyte part and a part relative to ions. The nonelectrolyte part is taken from the equations of state (EOS) of Schwartzentruber et al. (1989). The ionic part is composed of an MSA long-range term to account for electrostatic interactions and a short-range interaction term specific to ions. Using correlations between parameters and experimental ionic diameters, the model reduce to a one-parameter model. It has been applied to numerous strong electrolyte systems and extended to ternary systems to test its predictability without mixing parameters for ions. Its results compare well to the results reported for other one-parameter models (electrolyte EOS). Furthermore, it was found that the cation-anion interaction parameter could also be correlated to experimental ionic diameters. Then, the osmotic coefficients of 28 alkaline and alkaline-earth halide systems may be represented with a root mean square relative deviation of 2.9% using only six correlation parameters. This result has been extended to other systems, with the conclusion that the model with all parameters correlated may also be applied to systems other than halide solutions. The resulting model is predictive. The quality of the prediction was tested by determining osmotic coefficients relative to six systems without any parameter adjustment. The deviations of the predicted values range from 2.0 to 5.4%. The quality of the representation of mixed salts systems without mixing parameters was evaluated using experimental osmotic coefficients of 30 ternary systems.
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  • 8
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    AIChE Journal 39 (1993), S. 361-365 
    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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  • 9
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993) 
    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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  • 10
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 413-421 
    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 versatile and efficient method is developed for predicting dynamic performances of parallel and counterflow heat exchangers subject to arbitrary temperature variations and step flow disturbances, including the effect of flow maldistribution and the influence of heat capacities of both fluids, shell wall and tube bank as well as nonzero initial temperatures. Two algorithms of numerical inversion of the Laplace transform are introduced to determine the final temperature profiles in the realtime domain and some examples are calculated with nonuniform initial conditions. The accuracy of the proposed method is demonstrated with the calculated results at new steady states. Experiments are carried out on a labor-sized heat exchanger to further examine the feasibility of this method and the comparison between calculated and measured temperature profiles is illustrated and discussed.
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  • 11
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993) 
    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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  • 12
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 761-773 
    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 fundamental study was conducted on the effectiveness of the chemical calcium magnesium acetate (CMA) as a sulfur capture agent during combustion of pulverized coal. It was based on high-temperature laboratory-bench experiments with the scope of exploring the use of CMA as a “dry scrubbing” medium for in-boiler injection. Two methods of CMA introduction in the furnace were considered: dry-spraying fine powders of the chemical and wet-spraying aqueous solutions to generate fine aerosols. It considered conditions pertinent to post-flame in-boiler injection of CMA to identify optimum temperatures and residence times. In addition to the versatility of the water-soluble CMA to enable spray drying injection and therefore eliminate grinding costs, there are other attractive features. Mainly, its ability to form highly cenospheric, “popcorn” -like, oxide particles on heating to high temperatures. These cenospheres possess thin, porous walls with blowholes that enable penetration of the SO2 in the interior of the particle which promotes high sorbent utilization. SO2 captures in the order of 90% were achieved with dry-injection of the chemical at furnace gas temperatures of about 1,000° C, a Ca/S ratio of 2, and particle size of ≈ 50 μm. Moreover, CMA was superior(by over 40%) to either CaCO3 or Ca(OH)2 in sulfur capture effectiveness per unit mass of calcium. This commercially obtained CMA was even superior to reagent-grade calcium acetate (by as much as 30%), again per unit mass of calcium. The utilization of CMA and calcium acetate depended on the cenosphere wall thickness, rather than the particle size and, thus, outperformed other sorbents regardless of the size of the resulting oxide particles.
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  • 13
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    AIChE Journal 39 (1993), S. 809-819 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Using the equilibrium-dispersive model of chromatography, we have investigated recycling as a means to improve the recovery yields and possibly the production rates of chromatographic separations. When compared with the optimal values obtained for the conventional single-cycle regime, our results prove the potential for recycling in preparative chromatography. The analysis performed for the separation of two binary mixtures demonstrates that recycling not only improves the recovery yield but can increase the production rate under certain conditions. Different possibilities of collecting sufficiently separated fractions during recycling are compared. The mathematical model developed can be used effectively for designing optimal recycling strategies in preparative liquid chromatography.
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  • 14
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    AIChE Journal 39 (1993), S. 837-845 
    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 incompressible lattice-gas model by ten Brinke and Karasz is adopted to introduce the effect of specific interactions into a recently-presented Monte-Carlobased lattice expression for the Helmholtz energy of nonrandom mixing. While the lattice remains incompressible, intermolecular forces consist of two types: London dispersion forces and specific (chemical) forces. The specific interactions between similar components, as well as those between dissimilar components, are incorporated in a systematic manner. Closed-loop temperature-composition phase diagrams are obtained. The theory is compared with experimental data for several binary systems, including polymer solutions, which exhibit closed-loop coexistence curves. Theoretical and experimental results are in good agreement.
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  • 15
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    AIChE Journal 39 (1993), S. 876-884 
    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 nitrogen hyperfine splitting constant of ditertbutyl nitroxide radicals was measured with electron paramagnetic resonance spectroscopy at near-infinite dilution in near-critical and supercritical ethane, as well as in liquid propane, liquid isobutane, and several nonhydrogen bonding liquid solvents. While the measurements in the liquids are described well by the theory of McRae, large deviations from the liquid behavior are observed in supercritical ethane. The deviations are used as a measure of the effective local density of the solvent around the solute. At the two temperatures investigated, Tr = 1.009 and Tr = 1.084, the local density enhancement, defined as the ratio of local to bulk densities, exhibits a maximum of about 3 occurring around 1/2 the critical density. The maximum is removed well from the critical density, where the maximum of the isothermal compressibility is observed. Local density enhancements are short-range effects and do not correlate well with the development of long-range critical phenomena. Local density enhancement data in ethane are compared with the prewetting transition that has been observed in nearcritical ultrapure argon.
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  • 16
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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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  • 17
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    AIChE Journal 39 (1993), S. 899-903 
    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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  • 18
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    AIChE Journal 39 (1993), S. 918-923 
    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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  • 19
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    AIChE Journal 39 (1993), S. 731-732 
    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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  • 20
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    AIChE Journal 39 (1993), S. 1061-1071 
    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 Compare molecular dynamics and electron paramagnetic resonance spectroscopic experiments on very dilute solutions of nitroxide free radicals in nearcritical and supercritical ethane. The measurement of the effective local density of solvent in the cybotactic region of the probe solute shows that maxima in local density enhancements occur in both computer and spectroscopic experiments at about half of the critical density, well removed from the maximum in the solvent's isothermal compressibility.Remarkably, at the bulk density where the maximum enhancement occurs, we observed long-lived clusters in the vicinity of the solute molecule. Geometrically defined clusters persist for at least 100 picoseconds of simulated time. The persistence of these clusters is corroborated by the behavior of the solute diffusion coefficient, which shows fluctuating values over simulated time periods as long as 1.3 nanoseconds. We argue that fluctuations in the local solvent density about a solute molecule are not a long-ranged solvent critical effect. Rather, they represent a localized, short-ranged quasicritical phenomenon induced by the solute, which may be described in terms of a transition between weakly attractive and attractive behavior. We discuss the implications of time-varying microstructure for reactions in supercritical fluid media.
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  • 21
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    AIChE Journal 39 (1993), S. 1097-1098 
    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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  • 22
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    AIChE Journal 39 (1993), S. 1101-1106 
    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 gas-liquid slug flow pattern exists over a broad range of flow rate space at reduced gravity conditions and for that reason is expected to be widespread in many space applications. The objective of this work was to develop a model predicting the characteristics of slug flow at reduced gravity including the bubble length, shape, velocity and other properties of the slug flow. Observations derived from low-gravity experiments suggested the use of a boundary layer-type approach. Multiple solutions exist, and a criterion for selecting the solution which corresponds to experimental observation is indicated.
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  • 23
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    AIChE Journal 39 (1993), S. 846-854 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Giacomin and Oakley (1991) have shown that an upper convected Maxwell model with a structure-dependent relaxation spectrum incorporating the three-parameter kinetic rate equation proposed by Mewis and Denn (1983) works remarkably well for a molten LDPE in large-amplitude oscillatory shear (LAOS). In a search for a simpler framework for interpreting LAOS based on network theory, four nonlinear, differential constitutive equations, each with less than three parameters, were evaluated. These models are compared with the Mewis-Denn model, and a two-parameter model has been found to work just as well for molten IUPAC LDPE X. The LAOS behavior of molten LLDPE is also adequately described by this model.
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  • 24
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    AIChE Journal 39 (1993), S. 829-836 
    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 inaccessible porosity on the rate of gasification reactions is illustrated under conditions where intraparticle and extraparticle resistances to mass transfer are significant. The mathematical model developed here is based on a mass balance for the reactant fluid in the porous particle, coupled with an appropriate structural model developed for the kinetics-controlled case (Delikouras and Perlmutter, 1991). It is demonstrated numerically that the effects of inaccessible porosity generally diminish with increased diffusional resistances. In agreement with the prior kineticscontrolled case, it is shown that the effects of inaccessible porosity are more pronounced at lower values of the structural parameter ψ and at greater levels of the inaccessible fraction.
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    AIChE Journal 39 (1993), S. 908-912 
    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) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 924-924 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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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. 1292-1302 
    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 model presented for cross-flow filtration of liquid suspensions was formulated on the premise that among the particles convected to the filter medium surface in cross-flow filtration, only a fraction of them become deposited. A criterion based on the interplay of the geometry of the cake-suspension interface and various forces acting on a particle as it moves toward the interface was established and an expression of the adhesion probability of impacting particles developed. The model was then formulated by incorporating the adhesion probability information together with conventional cake filtration theories. Through sample calculations, the model was found to display behavior consistent with the observed phenomena of cross-flow filtration and capable of representing experimental results.
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    AIChE Journal 39 (1993), S. 1093-1096 
    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) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1113-1123 
    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 propagation of surface waves is investigated theoretically and experimentally for the case of a single layer of viscous liquid flowing down an inclined plane, where the plane is oscillating in the flow direction. This work focuses on the linearized wavemaker problem, where the oscillations create waves which are small perturbations from the undisturbed flow. Downstream from the entrance region to the incline where the fluid is introduced, the undisturbed interface is parallel to the incline surface, and theory predicts that oscillations do not interact with waves that travel along the free surface. These waves grow as if there were no oscillation at all, and their propagation is governed by a dispersion relation between frequency, wavelength, and wave growth for single layer flow down a nonoscillating inclined plane. The entrance region to the incline is therefore responsible for exciting the various wave frequencies which are observed down the incline, as well as the initial amplitude of these waves. Experiments performed verify that waves propagate as predicted. Theory indicates that these conclusions are valid when the oscillations are perpendicular to the incline, as well as for the case of multiple stacked layers.
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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
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    AIChE Journal 39 (1993) 
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    AIChE Journal 39 (1993), S. 1444-1454 
    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 kinetics of hydrogen absorption and desorption in LaNi4.8Al0.2,LaNi4.9Al0.1 and LaNi5, suspended in cyclohexane and LaNi5 in ethanol have been investigated. The absorption process can be described in terms of mass transfer and reaction resistances in series. The rate-limiting steps for this process are dissolution of hydrogen in the solvent and the reaction of hydrogen with the metal alloy. Over a broad range of hydrogen loadings, the reaction of hydrogen with the metal follows the rate equation:\documentclass{article}\pagestyle{empty}\begin{document}$$ R_{{\rm abs}} = k_a a_s \left({C_{{\rm H}_{2,S}} - C_{{\rm eq,}a}} \right) $$\end{document}This type of kinetic equation indicates that during hydride formation in a slurry a surface process is the rate-determining step, which was confirmed by the observed influence of the solvent. Desorption of hydrogen can be described best with a shrinking core relation:\documentclass{article}\pagestyle{empty}\begin{document}$$ 1 - \left({1 - X} \right)^{1/3} = k_d ln\left({\frac{{P_{eq,d}}}{{P_{H_2}}}} \right)t $$\end{document}The phase transformation at the β/α boundary appears to be the rate-determining step. Alloys with higher aluminum contents produce a lower reaction rate constant.
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    AIChE Journal 39 (1993), S. 1472-1482 
    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 growth kinetics and contact nucleation of calcite crystals were studied in a pH-stat crystallizer. Large seed crystals up to 230 μm were successfully prepared by the gel growth technique. The crystal growth data over a wide range of crystal sizes were evaluated from titration curves by an initial slope method and then analyzed by the two-step model. The mass-transfer and surface integration rates were found to be functions of crystal size with the exception of mass-transfer rates of small crystals less than 10 μm. The controlling step of crystal growth process was tested using the effectiveness factor concept. Large seed crystals of calcite induced contact nucleation when a stainless-steel impeller was used for agitation. The important features of contact nucleation for calcite crystals were explored and compared with those of soluble substances.
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    AIChE Journal 39 (1993), S. 1509-1518 
    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 study of diffusion and permeation of methane, nitrogen, and helium in miscible blends of poly(styrene-stat-acrylonitrile) (PSAN) and poly (methyl methacrylate) (PMMA) at 35-140°C shows that permeation coefficients (P) of helium followed the linear logarithmic mixing rule. Positive deviations from the linear logarithmic mixing rule were observed for permeation and diffusion coefficients (D) of methane and nitrogen below the glass transition temperature (Tg). The deviations decreased with increasing temperature and disappeared above Tg. The experimental results were analyzed by free volume and activated state theories. The Arrnenius plots of log D or log P vs. the reciprocal of temperature exhibited discontinuities in the glass transition region for all gases and blend compositions. The discontinuities are caused by large thermal expansion coefficient differences between the rubbery and glassy states of PSAN and PMMA. The sorption of methane in 50/50 PSAN/PMMA has dual-mode characteristics below Tg.
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    AIChE Journal 39 (1993), S. 1558-1562 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1261-1271 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Earlier work of Sinclair and Jackson on the flow of gas-particle suspensions in vertical pipes is extended to the case of ducts of arbitrary inclination. As a result of the compaction due to gravity, it is necessary to take into account forces transmitted between particles at points of sustained, rolling and sliding contact, and a simple frictional model of this contribution to the stress is introduced. The resulting theory is shown to predict fully developed flows with the qualitative features to be expected, even in horizontal ducts. The effects of flow rates, duct inclination, and duct width on the solution are explored.
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    AIChE Journal 39 (1993), S. 1303-1321 
    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 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 39 (1993), S. 1342-1354 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: N2O decomposition and formation during the oxidation of NH3 and HCN were studied in a quartz flow reactor in the presence of CO, NO and other gases. The emphasis is on the influence of CO and NO. In addition, the homogeneous nitrogen chemistry of fluidized bed combustion and the selective noncatalytic reduction of NO (SNR) are discussed. The rate of N2O decomposition in N2 agrees with a first-order rate expression. The presence of CO or H2 increases the decomposition rate regardless of the additional presence of O2For the formation of N2O, HCN oxidation is more efficient than NH3 oxidation. The presence of NO increases the amount of N2O formed during the oxidation of HCN or NH3.CO moves the N2O formation toward lower temperatures. H2O increases the reaction rate where few components are present, whereas H2O has little influence in the presence of large amounts of a combustible component such as CO. There are indications that NO is a necessary intermediate for any significant formation of N2O during the oxidation of NH3 and HCN. NO reduction is obtained when NO is initially present during oxidation of both NH3 and HCN. These results are comparable to the respective SNR results with reductant ammonia and urea.
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    AIChE Journal 39 (1993), S. 1370-1376 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The primary objective of this work was to demonstrate the conversion of scrap tires to activated carbon. We have been successful in this endeavor, producing carbons with surface areas greater than 500 m2/g and significant micropore volumes. Tire shreddings were pyrolyzed in batch reactors, and the pyrolysis chars activated by reaction with superheated steam. Solid products of pyrolysis and activation were studied with nitrogen adsorption techniques. We find that the porosity development during steam activation of tire pyrolysis char is similar to that reported for various other chars. A maximum in micropore volume is observed as a function of conversion, but the total surface area increases monotonically with conversion. We suggest that the activation process consists of micropore formation, followed by pore enlargement. The process conditions used in this study are a good starting point from which to optimize a process to convert tires to activated carbon.
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    AIChE Journal 39 (1993), S. 1406-1410 
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    AIChE Journal 39 (1993), S. 1415-1419 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1421-1430 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The influence of shear thinning and viscoelasticity on the power required for the mixing of viscous liquids using six different helical ribbon agitators has been investigated. Four Newtonian and 12 non-Newtonian fluids prepared using several polymers dissolved in varying concentrations in different solvents cover a wide range of rheological properties. By a careful choice of test media, the specific and combined effects of shear thinning and viscoelasticity on the power requirement have been examined. Simple models are proposed to predict the effective shear rate in the tank from the knowledge of the torque or power number. The effective shear rate predictions compared with the effective shear rate estimated using the scheme of Metzner and Otto (1957) show that they slightly depend on the shear thinning properties. Fluid's elasticity increases appreciably the power requirement, and departures from the generalized Newtonian power curve in the laminar regime are observed at smaller Reynolds numbers for viscoelastic fluids. Bottom wall resistance of the mixing vessel makes a negligible contribution to the power consumption.
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    AIChE Journal 39 (1993), S. 1455-1464 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Notes: A companion article (Chen and Hu, 1993a) discussed a statistical theory that for a system consisting of two closed subsystems, the residence time density (RTD) functions of the two subsystems will be statistically independent, if a two-dimensional perfect mixing exists at the subsystem boundary. In this case, the overall RTD function is related to that for individual subsystems through the convolution integral. This theory has been validated experimentally using two die-screw combinations.Based on this theory, a predictive RTD model for an intermeshing counterrotating twin-screw extruder has been developed. The screw in the longitudincl direction has been treated as C-chambers in series. The overall RTD of leakage flows has been calculated from the RTDs of these individual chambers and then converted into the RTD of the extruder. The predicted RTD has been tested against experimental results with success.
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    AIChE Journal 39 (1993), S. 1483-1496 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Separation of a binary mixture by a three-step one-column pressure swing adsorption process in isothermal and adiabatic cases has been studied. The separation performance of the process is characterized by three parameters: enrichment, recovery and productivity. It has been compared at various operating conditions. The evolution of the bed performance from cycle to cycle and the bed dynamics at cyclic steady state have also been addressed.
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    AIChE Journal 39 (1993), S. 1519-1526 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The linear chemical-physical theory (LCPT) model for liquid metal solution thermodynamics has been extended to the determination of the liquidus curves for binary intermetallic compound-forming systems. The equations developed include corrections to the observed melting point temperature and heat of fusion for compounds that dissociate partially on melting. The primary advantages of the LCPT model for solid-liquid equilibria are the small number of physically realistic parameters required, ease of implementation, and wide applicability. In addition, the model also permits the incorporation of compounds in modeling the liquidus curves that are not necessary for representing the liquid-phase thermodynamic properties. For the seven systems studied, the agreement between calculated and experimentally measured liquidus curves is quite good.
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    AIChE Journal 39 (1993), S. 1563-1568 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1574-1576 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1577-1577 
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    AIChE Journal 39 (1993), S. 1581-1591 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Lagrangian statistics are explored as a means of describing the transport of solids in a turbulently flowing liquid. The essential feature of the approach is to represent the concentration field as resulting from a distribution of sources of particles. It is argued that this provides a better framework to understand the physics than the Eulerian analysis currently being used. Fully developed concentration fields are calculated, using the assumptions of homogeneous turbulence and plug flow. It is found that the configuration of solids and the suspended load depend primarily on the ratio of the settling velocity to the friction velocity, which is a measure of the relative importance of turbulence and of settling in depositing particles. The analysis emphasizes the need for a better understanding of the mechanism and the rate of entrainment of particles into a turbulently flowing liquid.
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    AIChE Journal 39 (1993), S. 1611-1620 
    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 original technique for simultaneous measurements of concentration and velocity in a turbulent liquid flow with and without a chemical reaction is developed by combining a two-component He-Ne laser Doppler velocimeter with a Ar+ laserinduced fluorescence technique. The mass flux and eddy diffusivity of mass are estimated from the simultaneous measurements of concentration and velocity in a liquid shear-free mixing layer downstream of a turbulence grid. The results show that the present measuring technique enables us to simultaneously measure velocity and concentration with high resolutions and that the approximation of the mean gradient diffusion causes about 10% error in estimating the mass flux in a reacting liquid flow.
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    AIChE Journal 39 (1993), S. 1721-1725 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1726-1731 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1741-1753 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experiments were conducted with air-water flow in a horizontal 0.095-m pipeline at atmospheric pressure to examine the mechanism by which slugs form in a stratified flow. A specially designed entrance box was used to avoid disturbances. In these experiments, at superficial gas velocities less than 3 m/s, the slugs are found to evolve from waves, with a length of about 0.085 m, that are generated by a Jeffreys mechanism. These waves grow in height and eventually double in wavelength by a nonlinear resonance mechanism. Depending on the height of the liquid, the growth can lead to a breaking wave or to a wave that fills the whole pipe cross section. At superficial gas velocities equal to or greater than 4 m/s capillary-gravity waves with a wide range of lengths are generated by a linear Kelvin-Helmholtz mechanism. These rapidly evolve into long waves outside the range of linear instability. If the liquid height is large enough, these waves can form slugs through a nonlinear Kelvin-Helmholtz instability that is aided by wave coalescence.
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    AIChE Journal 39 (1993), S. 1810-1826 
    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 article, we approximate bounded operators by orthogonal expansion. The rate of convergence depends on the choice of basis functions. Markov-Laguerre functions give rapid convergence for open-loop stable systems with long delay. The Markov-Kautz model can be used for lightly damped systems, and a more general orthogonal expansion is developed for modeling multivariable systems with widely scattered poles. The finite impulse response model is a special case of these models. A-priori knowledge about dominant time constants, time delay and oscillatory modes is used to reduce the model complexity and to improve conditioning of the parameter estimation algorithm. Algorithms for predictive control are developed, as well as conditions for constraint compatibility, closed-loop stability and constraint satisfaction for the ideal case. An H∞-like design technique proposed guarantees robust stability in the presence of input constraints; output constraints may give “chatter.” A chatter-free algorithm is proposed.
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    AIChE Journal 39 (1993), S. 1859-1869 
    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 transport, wall deposition and evaporation of nanometer-sized aerosol particles are studied using a nonisothermal laminar flow in a pipe. The test aerosol particles, monodisperse Ag and NaCl particles of 7-40 nm dia., are introduced into a vertical circular pipe with wall temperature distribution in the axial direction. The measured particle loss during transport through the pipe increased with the wall temperature difference. The enhancement of particle loss due to diffusive and thermophoretic deposition is examined by the gas flow, temperature, and particle concentration distribution equations. Predicted particle losses agreed with the experimental results when the local variation of gas properties, particle Brownian diffusion, and thermophoretic migration are considered. Sudden increases in the particle loss due to particle evaporation were also observed at very high temperatures (about 700°C for Ag particles and 400°C for NaCl particles). The measured reductions of particle diameter due to evaporation showed good agreement with calculation based on aerosol evaporation theory for free-molecule regime.
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    AIChE Journal 39 (1993), S. 1966-1975 
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    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 39 (1993), S. 1995-2010 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Active cell migration is essential in many physiological processes and in the function of some bioartificial tissues. Therefore, several investigators have recently attempted to quantitatively characterize random cell movement on isotropic substrata in vitro. A popular approach is to fit a theoretical expression for mean-squared cell displacement deriving from correlated random walk models to cell tracking data, yielding three objective cell movement indices: root-mean-squared speed, directional persistence time, and random motility coefficient (analogous to a molecular diffusion coefficient). The data are obtained typically by averaging cell displacements over a cell track composed of cell positions measured at equal time increments and frequently by further pooling such displacement data from tracks of different cells from the same population. We identify pitfalls introduced if an ordinary nonlinear least-squares regression analysis is used to fit the theoretical expression to the data as is commonly done and propose a generalized least-squares regression analysis as a remedy. This method estimates the cell movement indices and associated uncertainties much more accurately. It also predicts the precision of the indices based on their assumed true values and provides a means to address such issues as optimal sampling methods for data acquisition from cell tracks and handling errors associated with measuring cell position.
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    AIChE Journal 39 (1993), S. 2042-2044 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 197-206 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A fractionation method for fine-particle suspensions using resonant ultrasonic fields coordinated with bidirectional fluid flow fields is described. The basis for the separation is differences in the speed of response of particles to the imposition of a resonant acoustic field. As such, the method is sensitive to the particle size and the acoustic contrast between the solid particles and their suspending fluid. Both batch and continuous fractionation processes can be developed from a two-step acoustic-flow cycle. An analytical model was constructed from equations that describe the trajectories of particles as they respond to the acoustic and flow fields. Model predictions indicate how the fractionation can be controlled through choice of cycle parameters. The method was implemented experimentally. Results for the fractionation of 325-mesh polystyrene spheres indicate that sharp fractionations can be achieved. The experimental results are generally in agreement with the model predictions.
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    AIChE Journal 39 (1993), S. 235-248 
    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 addition of cosolvents to supercritical fluid (SCF) solvents can have large effects on solubilities, giving engineers the ability to tailor loadings and selectivities of solutes for difficult separations. It is necessary to have a better understanding of the special intermolecular interactions that occur in SCF solutions to predict the effects of cosolvents. We use a SCF chromatographic technique to acquire a database of cosolvent effects for a variety of cosolvents and solutes; examination of the cosolvent effects shows evidence of hydrogen bonding, charge transfer complex formation, and dipole-dipole coupling between solute and cosolvent molecules. SCF solvents, carbon dioxide, ethane, and fluoroform, are compared, and then the use of the chromatograph to measure solubilities is discussed.
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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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    AIChE Journal 39 (1993), S. 387-396 
    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 calculate permeabilities for a class of granular porous media derived from a real, disordered packing of equal spheres. The entire structure, including pore space, of these media is completely specified by the radii and spatial locations of the constituent grains. When geometric nearest neighbor grains are grouped together, the structure may be subdivided into pore bodies and pore throats in a natural and unambiguous way. From this subdivision we can establish a network of flow paths whose geometry and topology are completely specified, so that permeability and other transport coefficients can be calculated directly and without any adjustable parameters. The calculations focus on processes that form porous media, rather than on specific examples of such media. Hence, the approach is essentially predictive, rather than correlative. No additional measurements (such as capillary pressure data or pore system data from thin sections) are required, and correlations between permeability and other properties are not used. Predicted permeabilities match measurements on sandstone samples similar to the model perous media studied here over a wide range of porosity. Geometrical attributes of the network representation of the pore space of the model media are found to be spatially correlated. This departure from randomness significantly affects permeability. The agreement between predictions and measurements suggests that spatial correlation is inherent in granular porous media and that uncorrelated network models are therefore unlikely to be physically representative of such media.
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    AIChE Journal 39 (1993), S. 369-386 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nonlinear transport processes in disordered systems such as porous media and heterogeneous solids are studied, which are represented by two- or three-dimensional networks of interconnected bonds, by a Bethe network (a branching network with no closed loops) of a given coordination number, or by a continuum in which circular or spherical inclusions have been inserted at random. The bonds represent the pores of the pore space, or the conducting and insulating regions of a disordered solid, to which we assign effective properties (radii or conductances) selected at random from a probability density function. Three types of nonlinear transport processes are considered. (1) The relation between the current q and the potential gradient v is of power-law type (as in, for example, flow of power-law fluids or the electric current in doped polycrystalline semiconductors). (2) The relation between q and v is piecewise linear, characterized by a threshold (as in flow of Bingham fluids or in mechanical or dielectric breakdown of composite solids). (3) A large v is imposed on the system, so that a linear transport theory is not valid. The behavioral study of the effective transport and topological properties of the system, such as the permeability, conductivity, diffusivity, and the shape of the samplespanning cluster of conducting paths shows that in all cases the concepts of percolation theory play a prominent role, even if the system is well connected and percolation may seem not to play any role. For most cases, new effective-medium approximations (EMAs) are derived for estimating effective transport properties. Compared to the case of linear transport, new EMAs are considerably more accurate in predicting the scaling properties of the transport coefficients near a critical point such as the percolation threshold. For a power-law transport process, an exact solution is also derived for the Bethe networks. Using the concepts of percolation theory, scaling laws relating the effective properties to various regimes of transport and to topological properties of the system are also given. A relation between the volumetric flow rate of a power-law fluid in porous media and the macroscopic pressure drop is derived, which contains no adjustable parameter and is valid at any porosity. To test the accuracy of our analytical predictions, Monte Carlo simulations are carried out for several cases. In most cases, good agreement is found between the simulation results and predictions. The extension of the results to other types of nonlinearities is also discussed.
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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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    AIChE Journal 39 (1993), S. 913-917 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    AIChE Journal 39 (1993), S. 925-934 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nuclear magnetic resonance (NMR) imaging techniques are used to determine porosity and saturation distributions. Difficulties in quantitation which arise from the short transverse relaxation times exhibited by fluids in porous media are addressed. Procedures are presented whereby transverse relaxation during the signal acquisition process is modeled to obtain accurate estimates of intrinsic magnetization intensity, and thus porosity and saturation. Special consideration is given to saturation/position dependence and multiexponential behavior of transverse relaxation. These procedures are validated with results for longitudinal profile images. The use of thin-slice cross-sectional profile images are demonstrated by observing fluid displacement in a rock sample with structural heterogeneities.
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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. 1007-1017 
    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 mathematical model is developed that predicts three-dimensional, two-phaseflow, heat transfer and reaction inside catalytic cracking riser-type reactors. The model consists of the full set of partial-differential equations that describe the conservation of mass, momentum, energy and chemical species for both phases in the reactor, coupled with empirical correlations concerning interphase friction, interphase heat-transfer and fluid-to-wall frictional forces. The cracking reaction is simulated by a simple three-lump kinetic model, but more realistic kinetic models can be easily included. The model can predict the most important engineering aspects of a riser reactor including pressure drop, catalyst holdup, interphase slip velocity, catalyst acceleration zone, choking behavior and temperature distribution in both phases, and yields distribution all over the reactor. It can also predict other complex engineering three-dimensional, two-phase problems realistically using computational fluid dynamics techniques.
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    AIChE Journal 39 (1993), S. 1087-1089 
    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. 1090-1092 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 1098-1099 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1107-1112 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An algebraic expression involving three universal constants is proposed for the eddy momentum diffusivity in fully developed turbulent pipe flow that adequately simulates its variation throughout the pipe cross-section. The model permits analytical integration to provide a single universal correlation that, unlike other available expressions, smoothly and accurately describes the entire turbulent velocity distribution from the inner region in the immediate vicinity of the wall all the way to the core region near the pipe axis and compares well with the existing correlations and experimental data. Accurate values of the maximum velocity and other flow variables of engineering interest can also be calculated from the velocity profile expression.
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    AIChE Journal 39 (1993), S. 1-1 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 178-187 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: 2-Chlorophenol (2CP) was oxidized in near-critical and supercritical water in a high-pressure plug-flow reactor. The global kinetics for 2CP disappearance were described by a rate law that was 0.88±0.06 order in 2CP, 0.41±0.12 order in O2, and 0.34±0.17 order in water. The activation energy was 11.0±3.8 kcal/mol, and the Arrhenius pre-exponential factor was 102.0±1.2 M-0.63 S-1. The uncertainties represent 95% confidence intervals. The products of 2CP oxidation included CO, CO2, HCl, other chlorophenols, chlorohydroxybenzaldehydes, dichlorophenoxyphenols, dichlorobiphenols, and chlorinated dibenzodioxins and dibenzofuran. The molar yields of the organic products were determined for a set of experiments at 380°C and 278 atm. The most abundant products were 2CP dimers such as dichlorophenoxyphenols and dichlorobiphenols, and the highest yield observed for any individual product was 0.6%. Although the yields of these products were low, their selectivities were high. For example, at 3.6 s, the shortest residence time studied under these conditions, about 50% of the carbon in the 2CP that reacted appeared in 2CP dimers, 18% appeared as CO2, and the balance (32%) was presumably in single-ring and ring-opening products. A reaction pathway analysis using the Delplot methodology revealed that the evolution of products from 2CP oxidation in supercritical water was consistent with a reaction network comprising two parallel primary reactions. One primary reaction path led to dichlorophenoxyphenols and dichlorobiphenols whereas the second primary reaction led to single-ring and ring-opening products. The 2CP dimers were convereted to single-ring and ring-opening products, which were, in turn, ultimately oxidized to CO2.
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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. 207-214 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Rheological behavior of moderately concentrated (up to 35 vol. %) suspensions or slurries prepared with non-Newtonian carrier fluids is investigated. Extensive experimental data on the Poiseuille slit flow of suspensions of sand in Hydroxypropyl Guar (HPG) solutions are presented. Flow data are gathered by pumping various non-Newtonian slurries into a unique, 8 ft (2.4 m) tall vertical apparatus, with great care taken to calibrate the instrument and to avoid settling difficulties. Investigated are the effects of polymer concentration, solids concentration, test temperature, and shear rate on the rheological properties of slurries. The rheological behavior of HPG solutions and HPG suspensions is characterized by a pseudoplastic power law non-Newtonian fluid model over a shear rate range of 30 to 500 s-1. The correlations for predicting the relative slurry viscosity for HPG fluids are presented. Substantial increase in viscosity of these non-Newtonian fluids is observed, and they are found to be a strong function of polymer concentration, shear rate, test temperature, and particle concentration. Results of this investigation are also compared with those available for Newtonian and non-Newtonian suspensions.
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    AIChE Journal 39 (1993), S. 27-36 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: There is as yet no theoretically sound and empirically proven procedure that is fully reliable for the design of thickeners. From a logical standpoint, a sound procedure is one correctly deduced from valid premises or assumptions. As noted in Fitch's earlier work(979), there is no reason to believe that existing mathematical models are based on uniformly valid assumptions. There is also much reason to believe that they are not. Therefore existing mathematical models or “theories” of thickening are analyzed for mathematical consistency, scientific credibility, and relevance to chemical engineering. Domains in which the models are useful approximations of reality and thus are relevant to chemical engineering practice are identified. Emendations or alternatives are suggested to bring the models more nearly into conformity with empirical results. Design procedures are suggested that, although involving assumptions that cannot be uniformly valid, would seem more reasonable than existing ones.
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    AIChE Journal 39 (1993), S. 111-126 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Free radical copolymerization in high-pressure autoclave reactors is studied by developing a mathematical model. Kinetic mechanisms to describe the polymerization rate, molecular weight averages, branching frequencies, as well as copolymer composition are presented. Two phase kinetics due to polymer-monomer solubilities in the reaction mixture are taken into account. Gel formation from cross-linking reactions is also analyzed. A mixing model is developed to represent the stirring effect inside the reactor. The mathematical model is implemented as a computer program to simulate commercial autoclave reactors. PID control equations are used to maintain operation at the unstable steady state. A sensitivity study is performed on the mixing model parameters and on some of the kinetic parameters and the model is compared to rate data from commercial reactors.
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    AIChE Journal 39 (1993), S. 189-192 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 149-162 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A nonintrusive technique for the in-situ measurement of interfacial pH and current efficiency has been developed. A ring electrode, operated potentiometrically at opencircuit, is used to measure the pH change at a rotating disk electrode. The technique takes advantage of the well-characterized hydrodynamics at the rotating disk electrode and has the added advantage that the pH probe, the ring electrode, is not interfering with the flow field and the current distribution on the disk. To determine the pH at the disk electrode by measuring the potential of the ring, the radial transport of hydronium ions across the insulating gap and on the ring is analyzed taking into account the effect of homogeneous dissociation reactions of water and metal-hydroxide ion complexes. Shifts in the ring potential caused by hydrogen super-saturation and ohmic drop are also evaluated. A platinized ring electrode in a hydrogensaturated electrolyte is shown to provide a stable and reproducible hydrogen ion sensor with a Nernstian response to the changes in the bulk pH. Performance of the ring is evaluated by generating hydrogen at the disk electrode from a dilute acid solution, in the absence of other electrochemical reactions. The technique is then applied to determine the interfacial pH of nickel, iron and nickel-iron alloy electrodeposition with concurrent hydrogen evolution. This method was also used to measure the current efficiency of nickel electrodeposition in a fast, nonintrusive and in-situ manner.
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    AIChE Journal 39 (1993), S. 193-196 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 367-368 
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    AIChE Journal 39 (1993), S. 434-445 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Modeling of reverse osmosis in the presence of strong solute-membrane affinity has always been a challenge due to the complexity of the solute-solvent-membrane interactions and the resultant effect on membrane performance. Most transport models, including all models treating membranes as nonporous and those based on irreversible thermodynamics, are unable to describe or to predict all of the phenomena associated with this case. Recently, the modified surface force-pore flow model has been derived and used to describe the performance of reverse osmosis membranes for solutes which are rejected from the membrane. In the present work, this model is extended to a more general form which can describe the solute-membrane affinity case. For illustration, the extended model, with five adjustable parameters, is used to describe the performance for cellulose acetate membranes and dilute aqueous solutions of toluene, cumene, and p-chlorophenol (data from literature). The model is reasonably consistent with the data. Simulation results of the extended model are also shown.
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    AIChE Journal 39 (1993), S. 581-588 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Unlike the traditionally fixed recipes in batch process operation, flexible recipes allow the adjustment of some of its relevant recipe items. These adjustments can either be predefined in cases of planned experimentation, or suggested by a formal process optimization or control algorithm on the basis of actual information. In both the response surface methodology and the simplex evolutionary operation (EVOP), some well-known methods for empirical model building and process optimization, flexible recipes are involved. Another application of flexible recipes arises in a feedforward quality control strategy of batch processes when variations in market or process conditions are known a priori. The experimental results of these strategies are presented for the batchwise production of benzylalcohol on a pilotplant scale. Experiments have been performed to obtain a reliable model of the yield. On the basis of this model, better process conditions have been suggested, which substantially deviate from the final simplex resulted from experiments within simplex EVOP. Finally, an adaptive feedforward control strategy has been applied for a priori known disturbances in the process inputs.
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    AIChE Journal 39 (1993), S. 625-635 
    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 solubility and diffusion coefficients of low-molecular-weight penetrants in a polymeric stationary phase were determined by use of inverse gas chromatography (IGC). Previously reported applications of packed-column IGC to the measurement of the stationary-phase diffusion coefficient have been carried out via the van Deemter approach. We present here a new mathematical model to describe the chromatographic process in packed columns. A moment analysis procedure was developed from this model to analyze the chromatographic peaks eluting from packed columns. The first moment (mean retention time) is determined to depend only on the equilibrium partition coefficient, whereas the second moment (variance) is related to both the thermodynamic and transport properties of the polymer-solute system. The validity of the technique was demonstrated by measuring the diffusivity and solubility of toluene and benzene in polystyrene above the glass transition temperature of the polymer. Free-volume theory was used to interpret and correlate the diffusivity data obtained at infinite dilution of the solute. One can use the results obtained at infinite dilution to predict reliably via the free-volume theory the concentration and temperature dependence of polymer-solvent diffusion coefficients.
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    AIChE Journal 39 (1993), S. 663-676 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Monte Carlo simulation results for binary mixtures of diatomic molecules with spheres, diatomic molecules of different bond lengths, and triatomic molecules with spheres, all interacting with the site-site Lennard-Jones potential, were obtained at three different volume ratios and a range of densities and compositions. We report the configurational internal energy of the mixture and of the 1-1, 1-2 and 2-2 pairs, and the compressibility factors at 195 state points. The site-site correlation functions also computed are available from the authors. Equations of state derived previously (Sowers and Sandler, 1991, 1992) for pure site-site Lennard-Jones fluids from a combination of perturbation theory and a three-parameter corresponding states principle are extended to mixtures using simple one-fluid mixing rules. These simple mixing rules allow us to make satisfactory predictions of the compressibilities computed from simulation without the use of binary interaction parameters. We also show that the effect of composition on the perturbation free energy βAp/N not accounted for by one-fluid mixing rules is quite small, and therefore a more complicated mixing rule is not necessary in our equations of state for the mixtures studied.
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    AIChE Journal 39 (1993), S. 698-700 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 714-714 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 695-697 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 95
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 715-719 
    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: 2 Tab.
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  • 96
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 730-731 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 97
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 1030-1044 
    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 conservation equation for the fluid concentration field during onedimensional viscoelastic diffusion is derived by retaining the concentration dependencies of physical properties in the fluid flux expression from the nonequilibrium thermodynamic treatment of Durning and Tabor (1986). The result is specialized to the limit of small, but finite, diffusion Deborah numbers to give a model essentially the same as that by Thomas and Windle (1982) for Case II transport (TW model). Orthogonal collocation on Hermite cubic trial functions together with a stiff ordinary differential equations integrator were used to solve the TW model for integral sorption in a dry film. The solutions show good agreement with previous analyses and confirm that strong nonlinearities in both the fluid diffusivity and the mixture viscosity are essential for prediction from the model of wave-like concentration profiles associated with the Case II process. Also, the numerical results partially confirm the analytical asymptotic analysis of Hui et al. (1987b) for the Case II wave-front velocity, v. They show that Hui et al.'s formula for the dependence of v on characteristic physical properties does not depend on the details of how the diffusivity and viscosity change with fluid content, as long as both are strongly nonlinear.
    Additional Material: 21 Ill.
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  • 98
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 733-744 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Macroscopic flow structures of gas-liquid and gas-liquid-solid fluidization systems are studied through flow visualization using a two-dimensional column under various operating conditions. The gas distributor in the column comprises multiple injectors which are individually regulated to generate desired gas flow rates, bubble injection frequencies, and bubble sizes. Colored bed particles and neutrally buoyant particles as solid and liquid tracers, respectively, are used for flow visualization through video photography. In a gas-liquid system operated under liquid-batch conditions, bubble streams injected near both sidewalls are observed to migrate toward bed vertical axis, and vortices appear along the sidewalls when gas velocity exceeds 4-6 mm/s. A considerable amount of liquid descends along the sidewalls in a vortical flow pattern. The gross circulation pattern occurring at high gas velocities is associated closely with induced liquid or liquid-solid flows resulting from rising bubbles and bubble wakes. When the gross circulation occurs, four flow regions can be distinguished. The formation of and mechanism for gross circulations can be interpreted in part based on two simplified flow conditions involving single bubbles rising in a stationary liquid and single chains of bubbles injected in a batch liquid. The effects of particle size, inlet liquid velocity and gas flow distribution on the macroscopic flow structure are also examined.
    Additional Material: 13 Ill.
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  • 99
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 797-808 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Column chromatography and electrophoresis are combined in electrochromatography, where an electric potential is applied to a chromatography column in the axial direction. These studies utilized a dextran gel stationary phase and an eluent of low ionic strength, which were chosen to minimize electric current and therefore column heating and undesirable dispersion effects. The gel, with a small ion exchange capacity of several microequivalents per mL, turned out to be more conductive than the eluent and was able to concentrate macromolecules in the presence of combined electric and flow fields. The model presented describes solute retention due to electrically induced concentration polarization of solute on the resin surfaces, as well as electrophoresis in the mobile and stationary phases. The polarization effect explains differences between retention of high-molecular-weight solutes with exclusion coefficients of less than 1 and that of a charged low-molecular-weight solute, which is hypothesized to pass through the gel matrix in the presence of an electric field and does not experience concentration polarization. It also shows the application of this effect for protein separation in a liquid chromatography system with a superimposed electric potential.
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  • 100
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 1124-1134 
    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-phase flow in porous media is described based on the extended form of Darcy's law, which ignores momentum transfer at fluid-fluid interfaces. Two forms of corrections to this simple description have been proposed in the literature: one on the relative permeability dependence on viscosity ratio; the other on the velocities assumed to be proportional to both phase pressure gradients and so introducing an additional saturation-dependent cross coefficient.In this article, to identify the correct form of transport equations, a simple cubic network model of 30 × 30 × 30 bonds is used. The cross section of the bonds is that of a four-cusp duct. The fluid interface in each duct is located by capillary equilibrium. The duct hydraulic conductances are then obtained as a function of viscosity ratio and phase volume fraction using a finite element calculation. These individual duct results are used in the network calculations for which a percolation algorithm is applied to simulate nonwetting phase displacing wetting phase, a process also known as initial drainage. Flow calculations show that both the nonwetting-phase relative permeability and the cross coefficient are strong functions of saturation and viscosity ratio. Also, the off-diagonal terms may contribute to a nonnegligible fraction of the flow. The proposed generalization of the Darcy equations is applicable to all problems involving multiphase flow in porous media. The current practices for relative permeability measurements and reservoir simulation may have to be reexamined in the context of the proposed transport equations.
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