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  • Chemical Engineering  (17,974)
  • Engineering General  (9,884)
  • 301
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1163-1170 
    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 hydrodynamic characteristics of a new type of reactor, the immobilized soil bioreactor, were studied. This apparatus is a practical new engineering concept (soil immobilization) based on entrapment of soil particles, which contain pollutant-degrading microorganisms, in the pores of a geotextile to activate the indigenous microorganisms. The soil immobilization is the third on the size scale of immobilization processes, coming after (1) that of molecules in heterogeneous catalysis (in Angstrom) and (2) that of microbial cells and their fragments in immobilized cells and enzymes biocatalysis (in micron). The size of immobilized soil particles is in the range of a millimeter. A mathematical model of liquid flow within the reactor is proposed, which qualitatively explains the distribution of the immobilized soil in space. The dynamics of soil immobilization within the bioreactor has been studied as a function of the particle size, initial slurry concentraion and air flow rate. A mathematical model of the process of soil immobilization was proposed based on deep filter mechanics. The process can be described by a second-order kinetic model. This study will be of great importance for the design of immobilized soil bioreactors for degradation of recalcitrant soil pollutants.
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  • 302
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1250-1264 
    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 systematic method that quantitatively assesses property prediction uncertainty (imprecision) on optimal molecular design problems is introduced. Propety-structure relations are described with specific nonlinear functionalities based on group contribution methods. Property prediction uncertainty is explicitly quantified by using multivariate probability density distributions to model the likelihood of different realizations of the group contribution parameters. Assuming stability of these probability distributions, a novel approach is introduced for transforming the original nonlinear stochastic formulation into a deterministic MINLP problem with linear binary and convex continuour parts with separability. The resulting convex MINLP formulation is solved to global optimality for molecular design problems involving many uncertain group contribution parameters. Results indicate the computtional tractability of the method and the profound effect that property prediction uncertainty may have in optimal molecular design. Specifically, trade-off curves between performance objectives, probabilities of meeting the objectives, and chances of satisfying design specifications offer a concise and systematic way to guide optimal molecular design in the face of property prediction uncertainty.
    Additional Material: 6 Ill.
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  • 303
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1287-1299 
    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 fugacity coefficients of the hydroperoxyl radical in supercritical water are estimated through molecular simulations. A potential function for the radical is first derived from ab initio self-consistent field molecular orbital calculations at the unrestricted Hartree-Fock level and from data in the literature. Molecular dynamics simulations of the hydroperoxyl radical are then performed in supercritical water and the fugacity coefficient of the radical is calculated by the free-energy perturbation method using the dynamic coupling parameter window-modification technique. The values of the fugacity coefficients at 773 K differ from unity. This methodology facilitates the incorporation of thermodynamic nonidealities in mechanism-based kinetic models for free-radical reactions in supercritical water.
    Additional Material: 6 Ill.
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  • 304
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2112-2122 
    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 of moisture in shrinking food gels during drying is studied based on a novel thermomechanical theory accounting for a structural transition in the material - from the rubbery to the galssy state - during drying. The proposed theory is applied to the drying of a model cylindrical starch-gluten gel system. The predicted drying characteristics depend on the Deborah number, a ratio of the characteristic relaxation time to the characteristic diffusion time. At low Deborah numbers, drying is Fickian. At intermediate and high Deborah numbers, however, drying is non-Fickian, leading to an apparent mass-transfer shutdown, which is a result of surface dryout and skin/shell formation. Based on a time-dependent surface boundary condition, the model proposes that surface drying is not only a function of the Biot number but also a function of the “Shell” number, a ratio of the Deborah and Biot numbers. The model is verified by comparing its predictions with experimental data from drying of starch-gluten gels at 22.5 and 40°C. The model predictions agree with experimental data and capture the observed sigmoidal shape of the experimental drying curves in the saturated flow regime. The predicted moisture profiles show shell formation and growth during drying, compatible with the experimental moisture profiles from the literature.
    Additional Material: 13 Ill.
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  • 305
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2148-2152 
    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: 4 Ill.
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  • 306
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2579-2595 
    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 comparison between experimental and theoretical results for the combined microwave and convective drying of softwood is presented. The microwave applicator used for the experiments was an oversized waveguide, and the results for both sapwood and heartwood were analyzed. To elucidate on the physics of the process at a fundamental level, a complete model is proposed, which considers the intricate link that transpires between the heat-and mass-transfer phenomena and the power distribution throughout the sample during drying. The resulting model, which uses a comprehensive 2-D set of equations to describe the drying process, together with a complete 3-D solution of the Maxwell equations within the waveguide in the time domain, can be used to investigate many aspects of dielectric drying. This research deals with the spatial variation of the power density within the material at various drying times and the effect of the anisotropy of the transfer properties on the shape and evolution of the power distribution. Most importantly, it focuses on the prediction of the location of hot spots and thermal runaway within the sample from the viewpoint of product quality. Strengths and weaknesses of the model are highlighted.
    Additional Material: 15 Ill.
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  • 307
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2903-2910 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To evaluate the effect of viscoelasticity on bubble formation, four rheological parameters of viscoelastic liquids were defined and measured by a rheometer. The effects of operating conditions and concentration of polyacrylamide aqueous solutions (PAA) as viscoelastic liquids on bubble volume and the growth curve were experimentally measured. A high-speed video camera showed that the shapes of a bubble growing in vis-coelastic liquids are not spherical. In this study, a nonspherical bubble formation model was proposed to theoretically estimate the volume, shape and growth curve of bubbles formed from an orifice submerged in viscoelastic liquids which are assumed to follow Maxwell's viscoelastic model. This experimental results in relatively low concentrations of PAA, as well as previous researchers' results, agreed relatively well with the calculated ones by this model.
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  • 308
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2944-2947 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: New correlations, based on the rough hard-sphere theory and an extensive literature database, were developed for the determination of the binary diffusion coefficients of liquid and solid solutes in supercritical solvents. The correlations were tested to predict 107 solute-solvent systems with good results. The input data required for the correlations are the solute molecular weight, temperature, density and the solvent basic properties (molecular weight, critical volume, and critical pressure).
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  • 309
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2984-2996 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Optimal thermodynamic feed conditions for distillation of ideal binary mixtures are identified through thermodynamic efficiency analysis of distillation columns. Due to simplifying assumptions, temperatures do not appear explicitly in the final thermodynamic efficiency equations. These equations are found to be functions of only feed composition, the thermodynamic state of the feed, and the relative volatility of the more volatile component A with respect to component B! When a single one-phase feed, AB, is used, the preferred state of the feed is all liquid when the amount of heavy component B is greater than 50% and is all uapor when the amount of volatile component A is greater than 50%. For a single two-phase feed, a simple heuristic is presented to adjust the liquid fraction of a given feed to maximize the thermodynamic efficiency of the distillation column. For most binary mixtures, two feeds with the same composition, but one saturated vapor and the other saturated liquid, can improve a distillation column's efficiency substantially. The maximum benefit is obtained for a 50-50 mixture. This two-feed case is less efficient than the single two-phase feed case when the relative volatilities exceed certain calculable values.
    Additional Material: 18 Ill.
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  • 310
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 3021-3030 
    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 optimal alarm-system design method, which takes full advantage of the inherent hardware and spatial redundancies in a mass-flow network, is proposed. In particular, systematic procedures are developed to identify independent measurement methods for the flow rate of any stream in the process and to synthesize corresponding alarm generation logic. To implement the suggested alarm strategy, the formulas for evaluating conditional probabilities of type I and II mistakes are also derived. The results of applying the proposed alarm system to the application example show that the approach taken in this work is effective in suppressing the latter mistakes. Further, this system is superior to any of the existing alarm techniques in the sense that it can be appropriately tailored to minimize the expected loss due to misjudgments in generating alarms.
    Additional Material: 6 Ill.
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  • 311
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 3085-3094 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Solid-solid combustion becomes self-sustaining when the preheating of the fresh mixture is high enough to support a spontaneous chemical reaction. These reactions have high activation energies, requiring significant preheating. Traditionally, conduction has been considered as the main form of preheating, and propagation velocities in the order of a few mm to a few cm per second were found. When acoustic equations are included in the analysis, no significant changes occur for traditional SHS reactions. However, the analysis of a 1-D model propagating at a constant velocity reveals the existence of two other solutions with propagation velocities which are much faster. An SHS deflagration wave is found with combustion temperature lower than the adiabatic value. The propagation velocity is less than the longitudinal sound speed of the medium, but typical Mach numbers vary between 0.6 and 0.95. The third solution is an SHS detonation with temperature above the adiabatic value and supersonic propagation velocity. Since the heat fluxes are extremely high, the hyperbolic conduction model is used.
    Additional Material: 7 Ill.
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  • 312
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 3105-3110 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To determine the behavior of hydrogen in tetralin, the reaction of tetralin with tritiated gaseous hydrogen was studied in a flow reactor at 400-450°C, 2.5-9.8 MPa for various residence times. The amount of hydrogen exchange between tetralin and tritiated hydrogen was estimated from the balance of hydrogen and tritium. Although yields of methylindan and naphthalene, and the hydrogen-exchange ratio (HER) of tetralin increased monotonously with residence time, these values were scarcely influenced by the reaction pressure at every temperature. It was thought that the formation of tetralyl radicals in this system would be the rate-determining step for both the conversions of tetralin into methylindan and naphthalene, and the hydrogen exchange of tetralin. Conversions of tetralin into methylindan and naphthalene, and the hydrogen-exchange reaction using the autoclave were very close to those using the flow reactor.
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  • 313
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    AIChE Journal 43 (1997), S. 3117-3120 
    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: 4 Ill.
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  • 314
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 3147-3160 
    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 modeling of pressure filtration of flocculated suspensions using compressional rheology and a knowledge of compressional yield stress Py(φ) and a hydraulic resistance factor r(φ)(φ is the local volume fraction of solids) is shown to yield an initial solids loading that maximizes the throughput of the filter. The optimal initial height h0 is such that the filtration time to reach a specified average volume fraction as output equals the handling time for the filter press. The maximum throughput of the press is then examined as a function of the remaining control parameters, the initial solids volume fraction φ0, and the applied piston pressure δP. The dependence of filtration time on φ0/∞00 (where φ∞is the volume fraction of solids at infinite time under applied pressure δP) enables the construction of a simple numerical model for the pressure filtration process, which accurately approximates predictions of the full compressional rheology model.
    Additional Material: 15 Ill.
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  • 315
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 3205-3214 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: For polymers and other homologous mixtures that span a molecular weight (MW) range, many reaction mechanisms involve the formation, addition and decomposition of free radicals. In the chain reactions of polymerization and depolymerization, radicals and polymer molecules interact by a variety of primary reactions. We postulate that these radicals and molecules can be described by continuous molecular weight distributions (MWDs). Their chemical interactions are developed from generic, reversible addition or bond scission reactions. Distribution balance equations are proposed for initiation-termination and propagation-depropagation reactions, such as hydrogen abstraction, disproportionation, chain cleavage, and radical coupling. A comprehensive model including all these events conforms to the special mechanisms for chain-end depolymer-ization and for random-scission polymer degradation. The evolution of an MWD from initial state to final equilibrium is described by the time dependence of MW moments. Irreversible degradation or polymerization relationships are obtained as limiting cases. First-order rate constants observed in pyrolysis and thermolysis reactions are composed of algebraic groups of primary reaction rate constants.
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  • 316
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    AIChE Journal 43 (1997), S. 3232-3240 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Immobilized metal ion affinity chromatography has shown promise for isolating desired proteins from host cell extracts, based on differential affinities for chelated metal ions. This article focuses on modeling the effect of loading pH on the purity and binding capacity of target proteins, during their separation from the cell extract of Escherichia coli, using immobilized copper affinity chromatography. Early chromatography experiments revealed that cellular proteins of E. coli elute in two separate peaks from an immobilized copper column under a decreasing pH step gradient. Thus, the cell extract is modeled by a mixture of two proteins, tuna heart cytochrome c and chicken egg white lysozyme. Transport and binding parameters of these proteins are evaluated over a wide pH range and used in a mathematical model of multicomponent chromatography. Target proteins are chosen such that they elute at a pH between the elution pH of cytochrome and lysozyme. Simulation results showed that decreasing the loading pH to a value between the elution pH of the weaker copper binding proteins of E. coli and that of the target protein may not only decrease the amount of E. coli proteins bound in the column but lead to a substantially higher binding capacity for the target protein.
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  • 317
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    AIChE Journal 43 (1997), S. 363-373 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Batchwise fluidized-bed calcination and sulfation of a limestone were done to investigate particle comminution phenomena and their relation with parallel occurrence of reactions. Operating conditions of the bed were those typical of atmospheric bubbling fluidized-bed combustors. A general framework of comminution phenomena is outlined, which includes different types of fragmentations as well as attrition by abrasion. Comminution processes were characterized by following the modifications of bed sorbent particle-size distribution and the elutriation rates of fines throughout conversion. Mutual interactions between comminution processes and the progress of chemical reactions are assessed.
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  • 318
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    AIChE Journal 43 (1997), S. 1-1 
    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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  • 319
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    AIChE Journal 43 (1997), S. 64-72 
    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 many instances of practical interest, countercurrent adsorption separations operate on feed streams containing not only the components to be separated but also some desorbent. Criteria for the optimal and robust design and operation of these units are developed by extending previous treatments developed for desorbent-free feedstreams. The effect of the presence of some desorbent (weak, intermediate, or strong) on the location and robustness of the region of complete separation in the operating parameter space is discussed.
    Additional Material: 7 Ill.
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  • 320
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    AIChE Journal 43 (1997), S. 91-103 
    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 method is presented to synthesize drowning-out crystallization-based separation schemes for binary mixtures. The method tracks how the composition of each process stream changes from unit to unit on a phase diagram by assuming that the system is at equilibrium. Features of phase behavior favorable to drowning-out processes are identified. Two types of systems are highlighted. In the first, the drowning-out agent causes the solute to become sparingly soluble. Several process alternatives to separate the feed into pure components are proposed. Dominant costs of each configuration are identified. In the second, the solute is extracted into a phase rich with respect to the drowning-out agent. The extraction can be performed in a decanter, countercurrent extractor, or fractional countercurrent extractor. Guidelines are given to select an extractor type and to choose between crystallizer-extractor and extractor-crystallizer equipment trains.
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  • 321
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    AIChE Journal 43 (1997), S. 135-144 
    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 acrylic acid (AA) solution polymerizations were characterized under various polymerization conditions using differential scanning calorimetry. The AA polymerization rate Rp decreased with increasing pH over all pH values due to the decreased reactivity of ionized AA relative to the unionized monomer. The rate behavior above pH 6 was suggestive of diffusion-controlled termination kinetics. The degree of ionization thus impacted not only the reactivity of species in solution but also the diffusive characteristics of propagating macroradicals. As the AA concentration was increased, the change in polymerization rate with pH was substantially less. The temperature dependence of Rp indicated that the overall activation energy for polymerization varied with temperature, due to diffusion-controlled termination kinetics. The polymerization rate was significantly higher when a multifunctional cross-linking agent was added, because of the gel effect, even while maintaining a constant double bond concentration.
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  • 322
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    AIChE Journal 43 (1997), S. 173-179 
    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 dolomitic calcine was hydrated with liquid water and then recalcined as an effective sorbent toward SO2 removal. The hydrated/recalcined sorbent was tested for SO2 removal in a thermogravimetric analyzer under conditions applicable to an atmospheric fluidized-bed combustor: 1,123 K, 20 vol. % excess air, and 3,000 ppmv SO2. Specific pore surface areas and volumes of hydrated/recalcined dolomites, hydrated at 80°C for 1 h, increased by four and five times, respectively, compared to unhydrated dolomitic calcines. Due to these improved pore characteristics, the SO2 capture achieved by the hydrated/recalcined calcine, was 1.3-1.6 times higher than that of the unhydrated one after a 1-h exposure to SO2 concentrations of 0.11-0.31 vol. % at 1,073-1,173 K. In the hydrated/recalcined calcine CaO utilization was enhanced due to the absence of significant pore diffusional limitations, at least during the early reaction times, evidenced by the high apparent activation energy of 198 kJ/mol. On the contrary, the lower CaO utilization in the unhydrated calcine was presumably due to severe pore diffusional limitations, which dropped the apparent activation energy from 149 to 85 kJ/mol at 〉 1,123 K.
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  • 323
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    AIChE Journal 43 (1997), S. 665-672 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: For an adequate model of the processes of compressible cake filtration and mechanical expression, permeability and compressibility data are required. Experimental and modeling results of the creep behavior of palm-oil filter cakes at constant and time-dependent pressures are presented. Creep curves of palm-oil filter cakes at constant pressures cannot be modeled with linear viscoelastic models. Modeling with a modified form of the empirical equation of Nutting gives satisfactory results. This modification does not lead to unrealistic values of the porosity at extreme conditions, contrary to the original form of the equation of Nutting. Creep curves at time-dependent pressures were modeled with two nonlinear viscoelastic models, which describe the time-dependent creep behavior as a function of the pressure history and creep curves at constant pressures. Modeling with the strain-hardening model provides the best porosity predictions.
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  • 324
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    AIChE Journal 43 (1997), S. 243-250 
    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 pure culture of Pseudomonas putida was grown as a film on carbon particles in a differential fluidized bed biofilm reactor, a new experimental system for the application of diffusion-reaction models. In the active biofilm, effective diffusion coefficients of the essential substrates - phenol and oxygen - were simultaneously calculated. The multisubstrate biokinetic expression used in the model solution was derived by nonlinear regression analysis of the data of continuous system fermenter experiments. The determined biokinetic equations were utilized to solve the diffusion-reaction model for effective diffusion coefficients in the active biofilm. The ratio of the evaluated effective diffusion coefficient through active biofilm to that of water varied between 17-44% and 9-24% for phenol and oxygen, respectively, for different biofilm densities. Results of the study showed a fair agreement with the literature at low biofilm densities.
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  • 325
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    AIChE Journal 43 (1997), S. 263-264 
    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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  • 326
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    AIChE Journal 43 (1997), S. 281-282 
    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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  • 327
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    AIChE Journal 43 (1997), S. 283-285 
    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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  • 328
    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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  • 329
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    AIChE Journal 43 (1997) 
    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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  • 330
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    AIChE Journal 43 (1997), S. 345-356 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pressure fluctuations in gas-solid fluidized beds have long been recognized as an important index for the quality of fluidization. Due to their highly random nature, many researchers have resorted to stochastic signal-processing methods to extract useful information. However, methods such as power-spectral density are based on a priori hypothesis of the stationarity of the signals, whose validity has not been investigated. In this article, using the Wigner distribution (WD), the signal's strong nonstationary feature is demonstrated and signal properties are addressed. Local frequency information is extracted from the defined parameter - the local peak weighted average (LPWA), which can be regarded as a generalized concept of the major frequency of power-spectral density in the nonstationary case. Experimental results indicate that LPWA is stochastically much more reproducible than the major frequency of power-spectral density. The change in LPWA under different operating conditions may reflect the corresponding change in the bubble phase. This information is useful in characterizing the quality of fluidization.
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  • 331
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    AIChE Journal 43 (1997), S. 409-418 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Resolution in chromatographic separations can be compromised by nonuniform flow distribution, heterogeneous packing, or flow instabilities such as viscous fingering. In this work, the displacement of solutes within a chromatographic column was monitored with an advanced magnetic-resonance technique, echo-planar spectroscopic imaging (EPSI). Unlike conventional magnetic-resonance imaging, this approach allows multiple solutes to be observed simultaneously, providing separate “chemical images” for each component. Qualitative chemical images were obtained in approximately 1 min with approximately 1 mm3 spatial resolution. EPSI allowed us to examine the multi-component viscous fingering problem for the first time. While many features of the instability are preserved, solute retention appears to slow the growth of solvent fingers.
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  • 332
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    AIChE Journal 43 (1997), S. 425-439 
    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 optimal control structure has been introduced as a design tool to measure the control-law nonlinearity of a given process design. In this context, control-law nonlinearity is the optimal degree of nonlinear compensation in the controller, a system property distinct from open-loop nonlinearity and determined by a performance objective and the region of operation as well as the nature of the open-loop system. This approach is extended to the analysis of multivariable systems with output feedback through the application of an extended Kalman filter. Coherence estimation is used as a practical method to measure continuous, open-loop multivariable system nonlinearity. The CSTR with van de Vusse kinetics, a system that features output feedback and a controllaw nonlinearity that changes with operating points, is analyzed. The optimal control structure approach with coherence estimation correctly indicates changes in the controllaw linearity between different operating points and changes as the regions of operation change around a particular operating point.
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  • 333
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    AIChE Journal 43 (1997), S. 486-494 
    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, heat transfer, and reaction in fluid catalytic-cracking riser-type reactors are studied using a 3-D mathematical model. This study was carried out based on the model of Theologos and Markatos, which incorporates a detailed ten-lump reaction kinetics scheme and accounts for gradual feedstock vaporization inside the reactor. Predictions obtained using the new model are compared against industrial reactor operating data. A design study was also carried out to illustrate that the model developed is capable of predicting feed-injector geometry effects on overall reactor performance. It shows that by increasing the number of feed-injection operating nozzles at the bottom of the reactor, selectivity of primary products is improved.
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  • 334
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    AIChE Journal 43 (1997), S. 1060-1068 
    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 application-oriented design procedure is presented for unique and point-stable operations of first-order reaction systems in a continuous stirred-tank reactor (CSTR). For a given set of values of kinetic constants, reaction enthalpy, feed conditions, residence time, and relevant physical properties, two boundary values of the heat-transfer capacity (St1, St3) and two of the modified coolant temperature (θmc, 2, θmc, 3) are analytically derived after a linearization of the unsteady mass and energy balances. With these boundary values, two separate design conditions are formulated; one for the heat-transfer capacity (HTC, characterized by St) and one for the modified coolant temperature (MCT, characterized by θmc). Each of these conditions is sufficient to guarantee unique and point-stable steady-state operations for a range of St or θmc values. Predicted behaviors of reacting systems are compared with experimental results obtained from five different systems reacting in four bench-scale and two commercial reactors.
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  • 335
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    AIChE Journal 43 (1997), S. 1041-1059 
    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 quantitative, model-based approach to the safety verification problem for general processing systems operating in the discrete time domain is presented. It is recognized that the operation of most of these systems involves both discrete and continuous characteristics. Therefore, an appropriate modeling framework is proposed, within which models of purely discrete, purely continuous and hybrid systems of arbitrary complexity can be constructed consistently. The models developed can then be incorporated into a safety verification formulation, which allows the identification of potential hazards that may occur while operating such systems, together with the combinations of events that lead to them. Apart from the dynamic process model, the data required for carrying out the analysis include the space of possible disturbances and the set of operating regimes that are considered to be unsafe or undesirable from the operability point of view. The formulation results in a mixed-integer optimization problem. A number of simple example problems presented illustrate the main ideas of the proposed technique, and the solution of an industrial-scale case study demonstrates its applicability.
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  • 336
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    AIChE Journal 43 (1997), S. 1100-1107 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: High-pressure homogenization is a key unit operation used to disrupt cells containing intracellular bioproducts. Modeling and optimization of this unit are restrained by a lack of information on the flow conditions within a homogenizer valve. A numerical investigation of the impinging radial jet within a homogenizer valve is presented. Results for a laminar and turbulent (k - ∊ turbulent model) jet are obtained using the PHOENICS finite-volume code. Experimental measurement of the stagnation region width and correlation of the cell disruption efficiency with jet stagnation pressure both indicate that the impinging jet in the homogenizer system examined is likely to be laminar under normal operating conditions. Correlation of disruption data with laminar stagnation pressure provides a better description of experimental variability than existing correlations using total pressure drop or the grouping 1/Y2h2.
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  • 337
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    AIChE Journal 43 (1997), S. 1265-1277 
    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 compartmental model is used to study imperfect mixing and its effects on polymer properties. Examples of imperfect feed mixing caused by a rapidly decomposing initiator are shown for styrene polymerization, high-pressure ethylene polymerization, and vinyl acetate/methyl methacrylate solution copolymerization. Continuation analysis indicates mixing can change reactor steady states and stability. A composite approach is proposed to construct full molecular weight distribution (MWD) under imperfect mixing. In linear polymerization imperfect mixing broadens MWD; however, in nonlinear polymerization mixing can cause either broader or narrower MWD. By changing the dominant chaintermination mechanism to chain transfer, the influence of imperfect mixing on the MWD can be reduced. Depending on reactivity ratio and monomer composition, mixing also affects copolymer composition and chain sequence length.
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  • 338
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    AIChE Journal 43 (1997) 
    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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  • 339
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    AIChE Journal 43 (1997), S. 555-564 
    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 study of the extraction characteristics of nitric acid with octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide [OφD(iB)CMPO or, simply, CMPO] was conducted. In the experimental program, CMPO was dissolved in n-dodecane to produce the organic extracting medium. The objectives of the project were to infer extraction stoichiometry and to estimate equilibrium constants for the extraction of nitric acid with the CMPO extractant.Experiments were performed over a limited range of concentrations to avoid conditions favoring formation of a third phase. Aqueous nitric acid concentrations were limited to 0.30 M at 25°C, 1.0 M at 40°C, and 3.0 M at 50°C. The data indicate that CMPO extracts nitric acid with a 1:1 stoichiometry. The value of the equilibrium constant is estimated at 2.66 ± 0.09 at 25°C. The enthalpy of the extraction is estimated to be - 5.46 ± 0.46 kcal/mol.
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  • 340
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    AIChE Journal 43 (1997), S. 565-576 
    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 phenomenon of colloidally induced fines migration is a challenge of both scientific and industrial importance. Its occurrence impacts permeability reduction and alteration of flow pathways in porous media, particulate contaminant migration in groundwater flow, and filtration. The release of smectitic fines is a threshold type of process resulting from discontinuous jumps, called microquakes in the interlayer spacing. There is a critical salt concentration at which these microquakes occur and produce fines migration in the porous media. The changes in the microstructure with decreasing salt concentration were analyzed using X-ray diffraction. The transition between crystalline and osmotic swelling regime is also shown to depend on the type of cation. A mathematical model developed using colloidal principles predicts the swelling behavior of smectites in aqueous solutions. The model can predict the transition of swelling from crystalline to osmotic regimes and explain the effect of different cations on the transition.
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  • 341
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    AIChE Journal 43 (1997), S. 588-597 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Numerical tools for the analysis of complex 3-D mixing devices were developed. Calculations are based on the finite-element method. The flow calculation is combined with that of pathlines for a fairly large number of material points; along these pathlines, relevant kinematic variables, which are then subjected to a statistical treatment, are evaluated. These numerical techniques are applied to the analysis of a Kenics mixer. It is assumed that the geometry is periodic in the axial direction, that is, that the mixer contains an infinite number of blades; the finite-element analysis may then be completed on a single wavelength of the geometry. To test the accuracy of the three-dimensional calculation, a Kenics device was mounted in order to mix clays of different colors, and photographs of experimental cross-sections were compared with numerical results showing concentration maps. A statistical treatment was performed on some 8,000 material points crossing the entry section to evaluate mixing quality.
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  • 342
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    AIChE Journal 43 (1997), S. 1436-1447 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Droplet breakup in laminar flows is important in emulsification processes and polymer blending. The influence of surfactants on droplet deformation and breakup in a plane hyperbolic flow was studied experimentally in an opposed-stream device. As in the case of simple shear flow, the inhomogeneity of the surfactant distribution along the droplet interface has a pronounced effect. Our results are qualitatively consistent with other numerical studies for droplet breakup in an axisymmetric elongational flow. Also a striking similarity is noted with other experimental observations for the deformation and breakup of polymeric drops in a quasi-steady-plane hyperbolic flow. The critical capillary number for droplet breakup in the experiments correlates with the interfacial viscoelasticity, and a reformulation of the numerical framework in terms of interfacial elasticity parameters is suggested for future numerical work including other linear flows.
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  • 343
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    AIChE Journal 43 (1997), S. 609-614 
    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 unsteady heat-transfer processes from oblate or prolate spheroids, at the limit of very small Peclet numbers is examined. A perturbation technique for the temperature and the geometry of the particle is used to obtain the rates of heat and mass transfer, first in the Laplace and then in the time domain. A solution to the problem is obtained, including the ∊2 contribution (∊ is the eccentricity). The solution reveals the existence of several history terms, which are analogous to the history terms of the creeping flow equation of motion. One of these terms is solely due to the eccentricity of the spheroid. This is an indication that the shape of the particle is a factor of the existence and from of history terms. In addition, an exact expression for the steady-state heat transfer from a spheroid is obtained using a convenient transformation of the heat-transfer integral.
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  • 344
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    AIChE Journal 43 (1997), S. 1849-1860 
    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 developed for SiO2 deposition in porous Vycor glass using SiCl4 hydrolysis describes reaction, diffusion and evolution of the pore structure due to accumulation of the solid product. The deposition reaction is described by transient heterogeneous kinetics in terms of the concentrations of silanol and chloride groups in the product layer as well as those of the gaseous reactants. For typical deposition conditions the pseudo steady-state approximation for surface species could lead to erroneous predictions. Pore structure evolution is modeled by incorporating results of percolation theory. For this purpose the porous glass is represented by a Bethe lattice with coordination number 3 and alternatively by a decorated Bethe lattice in which each bond is replaced by a composite bond consisting of two bonds in series. The second network can capture the effect of pore radius variation along a single pore. For the decorated lattice, pore connectivity interruption at a higher void fraction leads to thinner deposits and shorter deposition times for pore plugging compared to the corresponding ones for the simple lattice.
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  • 345
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    AIChE Journal 43 (1997), S. 837-843 
    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: 9 Ill.
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  • 346
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    AIChE Journal 43 (1997), S. 811-817 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Results from steady and unsteady, two-dimensional simulations of tertiary current distributions at and below the limiting current density are presented. The simulations are based on dilute-solution theory, with coupling of the concentrations of the ionic species through the electrical field. The electrical field is calculated from the electroneutrality constraint. Results confirm and extend previous theoretical predictions of the electricalmigration enhancement of the limiting current. To demonstrate the potential utility of general current-distribution solvers, measured temporal variations of the rate of copper deposition in the presence of an oscillating shear flow are measured and simulated. Experiments agree well with simulations.
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  • 347
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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: Transvascular and interstitial fluid movements are involved in many important biological processes such as convective macromolecular transport and contribute to the mechanical behavior of tissue. Although intimately coupled, there is a tendency in the literature to regard these two fluid-transport mechanisms separately; if the interaction is considered, the description is usually confined to the local level (e.g., transvascular or interstitial perivascular). A general framework presented here combines transvascular and interstitial fluid movement with the mechanics of soft tissue and integrates macro-and microscopic views of the phenomena. On the macroscopic level, interstitial fluid transport is described by adapting the field equations of the poroelastic theory using average field variables defined on a scale of several blood vessel diameters (∼ 1 mm), while transvascular transport is described by a generalized Starling's law. As an example, the model equations have been specialized for a spherical solid tumor and an analytical solution is presented for the transient redistribution of interstitial fluid following a rapid change in vascular pressure or flow. The model describes the overall average profiles of the interstitial fluid pressure and velocity, as well as the dilatation, displacement and stress of the solid matrix. Moreover, on a smaller length scale the model can describe the local fluid movement (perivascular) using the average field variables as boundary conditions. The basic theory provides new insight into understanding the fluid transport in biological tissues and a valuable tool for determining relevant fluid-transport parameters. Implications for improving drug delivery to solid tumors are also discussed.
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  • 348
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    AIChE Journal 43 (1997), S. 853-869 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Numerous experimental investigations on the vertical transport of dense gas-solid suspensions indicate that particles tend to segregate toward the tube wall. Although models based on the kinetic theory analogy can predict such patterns for perfectly elastic particle-particle collisions, the predictive ability of these models breaks down for inelastic collisions. In the present effort, a mathematical model is developed that incorporates two mechanisms that give rise to the lateral segregation of solids: interactions associated with individual particles based on a kinetic theory treatment and interactions associated with collections of particles based on an analogy with single-phase turbulent flows. Although these two mechanisms have been treated independently by previous workers, their combined contributions to the overall flow behavior have not been thoroughly investigated. The effect of such a treatment on the sensitivity of the model predictions to the inelasticity of particle-particle collisions is explored. A key element in eliminating the undue sensitivity appears to be a consideration of the effects associated with the collective motion of particles on the kinetic theory expressions. The resulting model can predict the expected segregation patterns for systems characterized by inelastic collisions, as well as many of the other salient features of vertical gas-solid flows.
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  • 349
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    AIChE Journal 43 (1997), S. 870-876 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mathematical models developed describe the unfolding of polymeric crystals in the presence of a solvent followed by their subsequent disentanglement. A thermodynamic model considering the free energy changes during crystal unfolding was proposed to obtain an expression for the unfolding rate. A simplified version of this expression, assuming uniform crystal size, was incorporated into a continuum model to predict the dissolution kinetics of a semicrystalline polymer slab. The model yielded predictions of the crystalline and solvent volume fractions as a function of position within the slab, in addition to changes in the fraction of polymer dissolved as well as the degree of crystallinity of the polymer as a function of time. The degree of crystallinity of the polymer decreased with time and the plot of the fraction of the polymer dissolved as a function of time exhibited Case II behavior. The model predictions agreed will with experimental results obtained during dissolution of semicrystalline poly(vinyl alcohol) in water.
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  • 350
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    AIChE Journal 43 (1997), S. 2559-2570 
    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 unsteady-state kinetics of NH3 adsorption-desorption and of selective catalytic reduction (SCR) of NO with NH3 were studied over model V2O5/TiO2 and V2O5-WO3/TiO2 catalysts by transient response techniques. Over both catalysts the dynamic experiments could be successfully described by a kinetic model assuming (1) negligible NO adsorption on the catalyst surface; (2) nonactivated NH3 adsorption; (3) a Temkin-type NH3 coverage dependence of the desorption energy; (4) a nonlinear dependence of the SCR reaction rate on the NH3 surface coverage. Thus, the results are supportive of an Eley-Rideal mechanism for the SCR reaction and of a significant heterogeneity for adsorption-desorption process and surface reaction of the catalyst surface. The binary and ternary catalysts exhibit similar acid properties, but different activity in the SCR reaction, possibly related to the superior redox properties of the WO3-containing sample. Over both samples the estimates of the activity energies for NH3 desorption at zero coverage and for the surface reaction of NO with NH3 are similar and in the 23-26 and 14-16 kcal/mol ranges, respectively.
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  • 351
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    AIChE Journal 43 (1997), S. 2246-2260 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Increasing automation in the CPI has led to the growing use of logic-based control systems (or safety interlock systems) in safety-related and sequencing operations. The growing complexity and safety-critical nature of typical applications make developing technologies for the formal verification of logic-based control systems with respect to their functionality a crucial and urgent issue. It still remains elusive to analysis, primarily due to the exponential growth of the alternatives that must be examined with application size. Implicit model checking is a formal verification technology that can be applied to the verification of large-scale logic-based control system. Its primary advantage is to formally verify large-scale coupled systems, where a novel and compact model formulation makes tractable previously inaccessible problems. Logic-based control systems are represented compactly as an implicit Boolean state-space model, and the properties to be verified are represented in the language of temporal logic. Verification is posed as a Boolean satisfiability problem and then transformed into its equivalent integer programming feasibility problem, which allows for efficient solution with standard branch-and-bound algorithms. Benefits of the methodology are demonstrated by applying to largescale industrial examples.
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  • 352
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    AIChE Journal 43 (1997), S. 2960-2969 
    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 algebraic solution for linear, ideal simulated moving-bed (SMB) chromatography derived previously revealed important new properties of the SMB process. This solution was validated by comparing with experimental data and with the results of numerical solutions of the equilibrium-dispersive and the lumped kinetic model. This earlier solution, however, was limited to the simple case in which the safety factor was assumed to be the same for the flow rates in all four sections. An extension of this solution to the case in which the safety factors differ and allow an independent selection of the four different flow rates (within limits) is derived. This solution accounts well for most practical situations. It permits the discussion of the influence of different flow rates on the performance of an SMB unit, an issue of critical importance for the optimization of the design and operation of these separators.
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  • 353
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    AIChE Journal 43 (1997), S. 3007-3020 
    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 two-level procedure for heat-exchanger network synthesis problems, which is related to structural optimization, is carried out by a simulated-annealing procedure. The main control parameters, that is, the initial annealing temperature, the temperature length, and the temperature-decreasing scheme, are extensively studied on the well-known 10SP1 problem, and their values are used for solving a 5SP1 problem with forbidden matches and a larger scale problem, the 20SP1. In all cases, the structural search is initialized with the network involving only utilities. For each generated network, the operating conditions (temperatures and split rates) are optimized by an NLP procedure to minimize the sum of investment and operating costs. Particular attention is given to the size reduction of the NLP problem. The proposed procedure leads to a reduction by a factor of 3 of the problem size in terms of number of variables and constraints. This slave problem is solved by an SQP procedure from the IMSL Library.
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  • 354
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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: Silicon-based microfabrication of a novel chemical reactor (microreactor) having submillimeter flow channels with integrated heaters, and flow and temperature sensors is described. The potential application of this reactor to partial-oxidation reactions is explored by using Pt-catalyzed NH3 oxidation as a model reaction. Investigation of reactor behavior as a function of operating conditions shows that conversion and selectivity behavior of conventional laboratory reactors can be reproduced and demonstrates the feasibility of conducting chemical reactions in microfabricated systems. Ignition-extinction behavior is explored, along with high-temperature microreactor materials degradation. Potential applications and scale-up of microreactors are also discussed.
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  • 355
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    AIChE Journal 43 (1997), S. 3111-3116 
    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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  • 356
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    AIChE Journal 43 (1997), S. 3121-3132 
    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 performance of the Kenics static mixer for mixing small streams of passive tracer into the bulk flow is investigated as a function of injection location and flow ratio. Flow ratios of 1/99 and 10/90 are simulated at nine different injection locations, and two alternative geometries are considered in addition to the standard Kenics mixer. Mixing is evaluated qualitatively by examining the spread of the tracer on cross-sectional slices from the mixer and quantitatively by computing the variation coefficient as a function of axial position. For the standard Kenics geometry, injection location strongly affects the extent of mixing only for the first few elements, after which the mixing rate is independent of injection location. In a sufficiently long mixer, material injected at any location spreads to the entire flow, but the least effective injection locations require up to four elements more than the most effective locations to achieve the same variation coefficient. A faster rate of decrease in variation coefficient is observed for a flow ratio of 1/99 us. 10/90. An alternative geometry in which the elements have 120° of twist instead of the standard 180° of twist shows a similar dependence on injection location and flow ratio, but is more energy-efficient than the standard Kenics geometry. In another alternative geometry in which all elements have the same direction of twist, segregated islands exist in the flow. For injection locations inside the segregated islands, virtually no mixing takes place; for injection locations outside of the segregated islands, the tracer spreads to the remaining flow but does not penetrate the islands.
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  • 357
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    AIChE Journal 43 (1997), S. 2385-2392 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Coalescence of electrolytically-generated, 50- to 600- μm-diameter gas bubbles was observed using an optical technique that employs a linear photodiode array to detect interface movement with a resolution of 10-6s. When two bubbles coalesce, the surface energy that is released causes interface velocities of 2 to 4 m/s; these are followed by large-amplitude damped oblate-prolate oscillations. Within the viscosity range studied, the oscillation period is insensitive to the viscosity and damping is insensitive to surface tension, in agreement with a scaling analysis based on a damped harmonic oscillator. Surface waves are superimposed on the motion. Finite-element solutions of the free-surface, nonlinear Navier-Stokes equations are consistent with the experiments.
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  • 358
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    AIChE Journal 43 (1997), S. 2405-2414 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dilute suspensions of neutrally buoyant, uniform-diameter spheres in a viscous liquid are sampled through pores in the wall of a stirred tank. These studies are performed to investigate screening effects near the sampling orifice that cause samples to be deficient in solids. The ratio of sphere concentration in the sample to that of the original suspension ranges from 0.08 to 1.12. Sample concentration decreases with decreasing sampling pore diameter and increasing stirring rates. The objectives of this work are both to obtain experimental relationships and to develop predictive techniques relating flow fields to sample concentration.Sample concentration is predicted by calculating particle trajectories in the region near the pore and by accounting for steric exclusion. Particle trajectories can differ from fluid streamlines due to lift forces generated in the flow field. These estimates constitute a priori predictions, since they do not rely on or introduce any empirical parameters. Predicted values of sample concentrations agree closely with data.
    Additional Material: 12 Ill.
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  • 359
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    AIChE Journal 43 (1997), S. 2432-2445 
    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 phase holdups and the heat-transfer behavior were studied experimentally in three-phase fluidized beds over a pressure range of 0.1-15.6 MPa. Bubble characteristics in the bed are examined by direct flow visualization. Pressure effects on the bubble coalescence and breakup are analyzed mechanistically. The study indicates that the pressure affects the hydrodynamics and heat-transfer properties of a three-phase fluidized bed significantly. The average bubble size decreases and the bubble-size distribution becomes narrower with an increase in pressure. The bubble-size reduction leads to an increase in the transition gas velocity from the dispersed bubble regime to the coalesced bubble regime, an increase in the gas holdup, and a decrease in the liquid and solids holdups. The pressure effect is insignificant above 6 MPa. The heat-transfer coefficient between an immersed surface and the bed increases to a maximum at pressure 6-8 MPa and then decreases with an increase in pressure at a given gas and liquid flow rate. This variation is attributed to the pressure effects on phase holdups and physical properties of the gas and liquid phases. A mechanistic analysis revealed that the major heat-transfer resistance in high-pressure three-phase fluidized beds resides in a liquid film surrounding the heat-transfer surface. An empirical correlation is proposed to predict the heat-transfer coefficient under high-pressure conditions.
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  • 360
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    AIChE Journal 43 (1997), S. 2446-2455 
    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 cyclones, the boundary layer formed on the collecting-wall surface acts as a barrier for particle migration toward the wall due to a decreased centrifugal force on particles inside the boundary layer. A new theory for high-efficiency cyclones based on the boundary-layer characteristics is presented. The cyclone was divided into two regions: the turbulent-core region where the centrifugal force is large, and the near-wall region where the centrifugal force is small. Particle trajectories in the turbulent-core region are calculated from the mean fluid motion based on the quasi-steady drag assumption, and the collection probability of particles in the near-wall region is calculated by the deposition velocity that results from both turbulent diffusion and centrifugal force. The deposition velocity by centrifugal force was assumed equal to the equilibrium migration velocity at a certain point inside the boundary layer, and the distance to that point from the wall is assumed to be linearly proportional to the dimensionless-particle relaxation time. When the proportional constant was determined by fitting the theoretical results to experimental data, the theory showed an excellent enhancement in predicting the variation of collection efficiency with the inlet flow velocity and particle size.
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  • 361
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    AIChE Journal 43 (1997), S. 2479-2487 
    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 model based on chemical reaction kinetics and diffusional mass transfer for the extraction of zinc sulfate with di(2-ethyhexyl) phosphoric acid (D2EHPA) in n-heptane at 250 C was developed. Gradients of the chemical potential were used as the driving force for diffusion. Activity coefficients and their derivatives were calculated from the Pitzer equation in the aqueous phase, while the organic non-ideality was considered by the Hildebrand-Scott treatment. The Nerst-Planck equation was chosen for describing the diffusion of aqueous ions, paying special care to the formation of hydrogen sulfate. It was assumed that this fast ionic reaction can be described in terms of the mass action law in the bulk and film. For the multicomponent mass transfer of the organic species, the Maxwell-Stefan theory was adopted. A kinetic equation for the extraction of zinc with D2EHPA, which considers the adsorption of the D2EHPA molecules at the interface based on the Langmuir law, was suitable for our experimental data. Organic zinc concentration vs. time was obtained in a type of Lewis cell with vibrational mixing. Molar fluxes were calculated by fitting it with rational functions, which were analytically differentiated. Initial conditions of the experiments cover a wide range of the zinc (0.1 mM to 0.05 M), D2EHPA, and sulfuric acid concentration. Experimental fluxes could be well described by this model when chemical kinetics and mass transfer were considered. In particular, the resistance to mass transfer in the organic film is important.
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  • 362
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    AIChE Journal 43 (1997), S. 2509-2523 
    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 of a six-bed, ten-step PSA operation is developed. The process cycle considered resembles an industrial hydrogen recovery process from the refinery fuel gas. Three hydrocarbon impurities (methane, ethane, and propane) are considered in the feed gas. The adsorbent used is activated carbon. The nonisothenmal, bulk separation PSA model adopts the linear driving force approximation for particle uptake and the extended Langmuir isotherm to represent adsorption equilibrium. A transient pressure equation is incorporated to account for the dynamics in uariable pressure steps. The model was verified using experimental results from a computer-controlled, laboratory-scale PSA unit. Considering the complexity of operation, comparison of various stream flow rates, concentrations, bed pressure and temperature profiles indicates that the model provides a sufficiently accurate prediction of the PSA performance. Parametric studies further show that its product purity declines relatively quickly with increasing cycle time and decreasing high operating pressure due to the breakthrough of a relatively sharp methane front. There is no real advantage in operating the PSA unit beyond a high operating pressure of about 18.0 bar.
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  • 363
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    AIChE Journal 43 (1997), S. 2524-2534 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Equilibrium, diffusion, and fixed-bed adsorption of n-hexane in pellets of 5A zeolite (Rhone-Poulenc) were studied between 373 and 573 K and at partial pressures up to 0.2 bar. Equilibrium data were obtained in a flow microbalance system. Diffusivity was studied simultaneously by gravimetric and ZLC techniques. Adsorption isotherms were satisfactorily described by a localized adsorption model developed by Nitta et al. (1984) with only one temperature-dependent parameter (coefficient of Henry's law). The isosteric heat of adsorption is 14.2 kcal/mol.Kinetic data clearly show that macropore diffusion is the controlling mass-transfer mechanism. Between 473 and 573 K, pore diffusivities range from 0.11 to 0.13 cm2/s in the system He-nC6, and from 0.06 to 0.08 cm2/s in the system N2C6. The effect of partial pressure of sorbate, temperature, and total flow rate in the behavior of the fixed-bed unit is shown. A simple mathematical model with equilibrium and diffusivity parameters obtained in this work predicts with good accuracy all fixed-bed adsorption experiments.
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  • 364
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    AIChE Journal 43 (1997), S. 2596-2600 
    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: 3 Ill.
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  • 365
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    AIChE Journal 43 (1997), S. 2605-2608 
    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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  • 366
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    AIChE Journal 43 (1997), S. 2911-2920 
    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 metering operation in the transfer-roll coating process is crucial for achieving a good uniformity and suitable thickness of the coating film. Experimental results carried out on a laboratory coater are reported. This coater mimics industrial flow conditions: it has a transfer roll and a metering-rod diameter similar to those found on a pilot coater, it operates at commercial speed, and the cover of the transfer roll is deformable. The experimental apparatus is described first. Then, a video analysis of the rib pattern is presented. Some interesting features are shown, in particular the existence of an inertia regime at high speed. The nip flow hydrodynamics are investigated using measurements of the pressure profile. It is shown that the film stability is strongly linked to the flow at the exit of the nip. The analysis of the maximum pressure in the nip, for various fluid viscosities and operating parameters, is represented using a master curve.
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  • 367
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    AIChE Journal 43 (1997), S. 2948-2959 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Transport models of diffusion-induced bubble growth and collapse in viscous liquids are developed and evaluated. A rigorous model for these important phenomena is formulated taking into account convective and diffusive mass transport, surface tension, and viscous and inertial effects. Predictions for bubble growth dynamics demonstrate the importance of viscous effects in the liquid surrounding the bubble for a wide range of conditions having relevance to polymer processing operations. It is also shown how previous models employing various approximations can be derived from the rigorous model by using different mathematical methods and dimensional analysis. Predicted bubble growth dynamics from the rigorous and approximate models are compared to establish the ranges of validity for two commonly used approximations. These comparisons indicate that models using a thin boundary-layer approximation have a rather limited range of applicability. A new approximate model, based on a previously published result, gives reasonably accurate bubble growth rate predictions with a significant reduction in computational effort.
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  • 368
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    AIChE Journal 43 (1997), S. 2997-3006 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Based on the absolute-rate theory, a consistent interpretation was provided for the dependence of surface-diffusion coefficient, Ds, on temperature and the amount adsorbed in various liquid-phase adsorption systems, such as the Langmuir-, Freundlich-and Jossens-type adsorption. It was demonstrated that a restricted molecular diffusion model for surface diffusion was useful for the analysis of the characteristic features of Ds. A formulation of Ds was derived based on the model and was applied to the analysis of surface-diffusion phenomena in various adsorption systems. The temperature dependence could be interpreted by assuming surface diffusion as an activated process. By taking into account the change in both the logarithmic slope of an adsorption isotherm and an adsorption potential, the concentration dependence of Ds could be interpreted irrespective of the type of the adsorption isotherms.
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  • 369
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    AIChE Journal 43 (1997), S. 2857-2864 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Elemental depth profile examined using secondary-ion mass spectroscopy and structural profile examined using grazing-incident X-ray diffractometry were applied to analyze the growth behavior of Pb1-xLax(ZryTi1-y)O3 (PLZTO) and Pb1-xLaxTiO3 (PLTO) thin films deposited on a Si substrate. When deposited under a suitably high substrate temperature, the chamber's oxygen pressure was observed to substantially influence the structure of the films. Low oxygen pressures (PO2 〈 0.01 mbar) deteriorate crystal structure without altering the composition of the films. Deposition of a buffer layer enhanced the formation kinetics of PLZTO and PLTO films. However, sufficiently thick SrTiO3 (∼500 nm) layer was required to achieve this effect. Using (La0.5Sr0.5)CoO3/Pt materials as double-layer electrodes not only prevented the film-to-substrate interaction, but resulted in preferentially oriented thin films. Ferroelectric properties of the films were thus greatly improved, with remanent polarization (Pr) around 14 ∼ 16 μC/cm2, coercive force (Ec) around 50 ∼ 60 kV/cm, and relative dielectric constant (ε) around 900 ∼ 1,000.
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  • 370
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    AIChE Journal 43 (1997), S. 2650-2656 
    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 process for synthesis of ultrafine ceramic particles using a high-temperature flame is described. Thermodynamic calculations for the Si-C-O-H system were performed using a computer program for calculation of complex chemical equilibrium compositions. Possible synthesis of ultrafine SiC partcles using Si, SiO, and SiO2 powders (1.0-3.0 μm) as Si sources was investigated using an electric furnace (5 kW) at 2,018 K. Particle products were characterized mainly by X-ray diffraction analysis, field emission scanning electron microscopy, and thermogravimetry-differential thermal analysis. Ultrafine particles (18-29 nm) of cubic SiC (β-SiC) could be produced through Si + CH4, SiO + CH4 and SiO2 + CH4 reaction systems, respectively. The effect of hydrogen addition on the synthesis of SiC was also investigated. Ultrafine particles of 96.0% SiC selectivity were obtained when H2 was added to the SiO + CH4 reaction system, and the CH4/SiO molar ratio in this case was 2.0.
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  • 371
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    AIChE Journal 43 (1997), S. 2670-2678 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experimental investigations of high-temperature kinetics of Si-precursor molecules relevant to CVD and ceramic processing are described. Reaction systems using SiH4, Si2H6, and SiCl4 highly diluted in argon were studied in a shock tube, a high-temperature wave reactor, by monitoring in situ the concentrations of atomic or radical reactants Si, H, Cl, SiH, and SiH2. Because of the very high dilution, the measured properties are sensitive to a limited number of elementary reactions, allowing a relatively direct determination of the respective rate coefficients. Both thermal pyrolysis and laser flash photolysis methods were used to expand the investigated temperature range. An overview of the bimolecular Si-atom reactions is given.
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  • 372
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    AIChE Journal 43 (1997), S. 2741-2750 
    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 partial oxidation of methane to synthesis gas (syngas, CO + H2) was performed in a mixed-conducting perovskite dense membrane reactor at 850°C, in which oxygen was separated from air and simultaneously fed into the methane stream. Steady-state oxygen permeation rates for La1-xA′xFe0.8 Co0.2O3-δ perovskite membranes in nonreacting air/helium experiments were in the order of A′x = Ba0.8 〉 Ba0.6 〉 Ca0.6 〉 Sr0.6. Deep oxidation products were obtained from a La0.2 Ba0.8 Fe0.8 Co0.2 O3-δ disk-shaped membrane reactor without catalyst, with a 4.6% CH4 inlet stream. These products were further reformed to syngas when a downstream catalytic bed was added. Packing the 5% Ni/Al2O3 catalyst directly on the membrane reaction-side surface resulted in a slow fivefold increase in O2 permeation, and a fourfold increase in CH4 conversion. XRD, EDS, and SEM analyses revealed structure and composition changes on the membrane surfaces. Oxygen continuously transported from the air side appeared to stabilize the membrane interior, and the reactor was operated for up to 850 h.
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  • 373
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    AIChE Journal 43 (1997), S. 2751-2759 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dense intermetallic and ceramic (alumina based) coatings can be formed in situ during simultaneous combustion synthesis and densification in the field of centrifugal forces. Both microstructure and composition of alumina-based coatings formed during alumino-thermal reduction of oxides can be altered by an introduction of additives such as ZrSiO4, SiO2, Na2CrO4, and carbon. The activation energy and frequency factor for the Ni-Al reacting system consisting of equal atomic amounts of Ni and Al powders with an average particle size of 5 μm were measured using a nonisothermal technique, which were equal to 1.05 × 105 J/mol and 1.017 × 108 s-1, respectively. A mathematical model of in-situ densification of a single-phase combustion product (NiAl) in the field of centrifugal forces was developed and explored.
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  • 374
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    AIChE Journal 43 (1997), S. 2793-2801 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Hexagonally-packed mesoporous Nb-doped silica molecular sieves were hydrothermally synthesized with various siliceous sources and dopant concentration levels. The microstructure of mesoporous materials was characterized by a variety of physico-chemical methods. The pore packing order of the Nb-doped material depended strongly on the synthesis conditions such as aging temperature, pH of reaction mixture, surfactantto-Si ratio, and dopant concentration. Different silica precursors gave rise to different reactivity with the Nb dopants and interactions with the surfactants. The pore size and surface area of the materials can be systematically varied. The chemical environment of the Nb dopants in the silica framework was studied by XPS, EPR, PA-FTIR, UV-Vis, and 29Si MAS NMR. The results indicated that the Nb5+ ions were well dispersed in the framework of the mesoporous silica. The diffuse-reflectance UV-Vis spectrum of the mesoporous Nb-doped silica is red-shifted with respect to pure mesoporous silica. The 29Si MAS NMR spectrum contained a broad component at about -105 ppm, which may have been attributed to the presence of Nb-O-Si bonding in the mesostructure.
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  • 375
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    AIChE Journal 43 (1997), S. 3070-3084 
    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 coal-fired combustion systems solid calcium species may be present as ash components or limestone added to the combustion chamber. In this study heterogeneous reactions involving HCN over seven different limestones were investigated in a laboratory fixed-bed quartz reactor at 873-1,173 K. Calcined limestone is an effective catalyst for oxidation of HCN. Under conditions with complete conversion of HCN at O2 concentrations above about 5,000 ppmv the selectivity for formation of NO and N2O is 50-70% and below 5%, respectively. Nitric oxide can be reduced by HCN to N2 in the absence of O2 and to N2 and N2O in the presence of O2. At low O2 concentrations or low temperatures, HCN may react with CaO, forming calcium cyanamide, CaCN2. The selectivities for formation of NO and N2O from oxidation of CaCN2 is 20-25% for both species. The catalytic activity of limestone for oxidation of HCN decreases with increasing degree of sulfation. Simultaneously the selectivity for formation of NO decreases while tht for N2O increases. The catalytic activity of sulfated limestone in-creases with decreasing SO2 concentration, indicating a competition between SO2 and HCN for sites on the surface. The results indicate that heterogeneous oxidation of HCN is important in calciners and fluidized-bed combustors with limestone addition or when burning coals with an ash with a high catalytic activity.
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  • 376
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    AIChE Journal 43 (1997), S. 3161-3174 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Plantwide control involves the systems and strategies required to control an entire chemical plant consisting of many interconnected unit operations. A general heuristic design procedure is presented that generates an effective plantwide control structure for an entire complex process flowsheet and not simply individual units. The nine steps of the proposed procedure center around the fundamental principles of plantwide control: energy management; production rate; product quality; operational, environmental and safety constraints; liquid-level and gas-pressure inventories; makeup of reactants; component balances; and economic or process optimization. Application of the procedure is illustrated with three industrial examples: the vinyl acetate monomer process, the Eastman plantwide-control process, and the HDA process.
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  • 377
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    AIChE Journal 43 (1997), S. 3193-3204 
    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 solving large simulation problems using Newton's method, a large sparse linear system Ax = b has to be solved. The cost of solving its problems can dominate the overall solution cost of the problem. Current approaches of reducing these costs are reviewed, and then a new algorithm for preordering the sparse matrix A is described that is based on the hierarchical structure provided by an object-oriented description of many recent modeling systems such as ASCEND, gPROMS, DIVA, and Omola. Particularly, rapid preorderings are obtained to support interactive manipulation of models and efficient solutions in automatic process synthesis algorithms, two applications where the preordering cost will be spread over only a few factorizations. With a factorization routine that permits a-priori reorderings (LU1SOL), this algorithm produces order of magnitude reductions in analysis and factoring times as well as in fill and operation count over our previous experience. The time to factor the 50,000 Newton equations for a highly recycled ethylene plant model is of the order of a few seconds on a conventional workstation. Abstracting and applying the fundamental concepts of this algorithm made it possible to improve the performance of the ma28 code significantly. This approach makes solution speeds competitive with and generally more consistent than codes considered the state-of-the-art (ma48 and umfpack 1.0).
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  • 378
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    AIChE Journal 43 (1997), S. 3274-3274 
    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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  • 379
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    AIChE Journal 43 (1997), S. 3264-3270 
    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: 7 Ill.
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  • 380
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    AIChE Journal 43 (1997) 
    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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  • 381
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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 variation of crystal system and conduction behavior of perovskite superconductor, BaPb0.75Bi0.25O3-δ, with oxygen deficiency was studied. The crystal system of BaPb0.75Bi0.25O3-δ changed from orthorhombic through tetragonal to pseudo-cubic as δ increases. The superconducting transition was observed in the specimens with the orthorhombic phase. Oxygen-deficient specimens with tetragonal or pseudo-cubic symmetry did not show a superconducting transition. The increase in electrical resistivity was also observed with an increase in δ. which suggested decrease of electron carrier mobility with the increase in δ. This effect of oxygen deficiency on conduction behavior of BaPb0.75Bi0.25O3-δ showed contrast with those of the superconducting cuprates, in which carrier concentration is affected instead of carrier mobility. The difference in the effects of oxygen deficiency on conduction behavior could be attributed to the difference of crystal structure between BaPb0.75Bi0.25O3-δ and superconducting cuprates.
    Additional Material: 6 Ill.
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  • 382
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    AIChE Journal 43 (1997), S. 13-24 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In most industrial gas-phase polyethylene reactors, heat is removed by cooling the recycle gas stream in an external heat exchanger, where a portion of the vapor is condensed. The condensate evaporates in the reactor to absorb heat released by polymerization reactions, thereby increasing the production capacity of the unit. Nonequilibrium methods of multicomponent condensation are applied to develop a 1-D model to simulate the cooling unit of an industrial polyethylene reactor system operated in partial condensing mode. Finite difference approximations are used to convert the resulting set of differential equations to algebraic equations. A practical method of solving the equations is to combine the rapid local convergence of Newton's method with a globally convergent strategy. Correlation methods for estimating local heat-transfer coefficients in the liquid film layer are discussed. Butterworth's method for shear-stress-controlled condensate flow gives reasonable agreement between simulation results and industrial data, while Chen et al.'s method can better describe the transition process of condensate flow from laminar to turbulent flow.
    Additional Material: 8 Ill.
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  • 383
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Ion-exchange processes involving weak electrolytes are influenced strongly by the pH via the occurrence of association/dissociation equilibria. This influence was investigated quantitatively through binary displacement experiments with different electrolytes to gain better insight in the role of the pH and to test a fixed-bed ion-exchange model used for the description of multicomponent processes. The two major factors determining the ion-exchange behavior of weak electrolytes are the actual exchange of counterions and the sorption of neutral species. The sorption of neutral species resulted in concentration fluctuations superimposed on the normal ion-exchange profiles, whereas pH fluctuations inherent to ion-exchange processes in general also influenced concentration through modified ionic fractions. The relative importance of these contributions is determined by the magnitude of parameters such as resin capacity, distribution coefficients of neutral species, and selectivities of ions, as well as by operating conditions such as concentrations of all species.
    Additional Material: 6 Ill.
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  • 384
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 703-714 
    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 trade-off between model accuracy and computation tractability for model-based control applications is well known. While nonlinear models are needed to capture the detailed behavior of many chemical processes, the resultant structures may not lead to straightforward control implementation. The current work advocates the use of low-order nonlinear models based on wave propagation that are mathematically concise and capture the essential nonlinear behavior of a process. In this work, differential geometry is invoked to achieve input-output linearization of a high-purity distillation column based on a traveling-wave model. A Kalman filter is used to recursively update the parameter values. Comparison with a linear controller based on a two-time constant model shows that the nonlinear controller outperforms the linear controller in tight control of both the overhead and the bottoms composition.
    Additional Material: 13 Ill.
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  • 385
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    AIChE Journal 43 (1997), S. 847-850 
    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: 3 Ill.
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  • 386
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 877-892 
    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-dimensional time-dependent calculations for a molecular model of finite extensibility in the journal-bearing geometry are presented. The flow is considered to be incompressible and isothermal. The momentum conservation equation is integrated using a time-marching procedure in which local ensembles of dumbbells act as stress calculators. The calculations are based on the Calculation of non-Newtonian flows: finite elements and stochastic simulation technique (CONNFFESSIT) and combine deterministic (finite elements) and stochastic techniques to advance the velocity and stress fields in time. The ability of CONNFFESSIT to treat models for which no closed-form constitutive equation can be derived is illustrated by performing calculations using FENE dumbbells. Significant differences in the stress field between the true FENE and the linearized FENE-P are found, especially during the inception period. Steady-state kinematics are, however, identical within error bars for both FENE and FENE-P and for the Newtonian fluid. The essential algorithm of 2-D CONNFFESSIT is detailed, as well as experience gathered from its parallel and vector versions.
    Additional Material: 15 Ill.
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  • 387
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    AIChE Journal 43 (1997), S. 1300-1308 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Initiaton of incrustation by crystallization mechanisms is studied. An experimental technique was developed by which nucleation of a crystalline phase on a solid surface is investigated at controlled local supersaturation without the interference of particle deposition. Experiments were carried out with different substances and surface materials. The results show that the solid surface may catalyze primary nucleation and hence promote the initiation of incrustation, but this was recorded only at quite high supersaturation. Collision of crystals with the solid surface in a supersaturated solution may initiate incrustation at a reasonably low supersaturation and can be of substantial industrial importance.
    Additional Material: 8 Ill.
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  • 388
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It is now well confirmed that the influence of temperature on the fall-off behavior of dissociation, recombination and chemically-activated reactions can be dramatic. For single-well, single-product dissociation reactions, it is customary to approximate these fall-off surfaces using extensions of Lindemann's empirical expression. We consider here chemical-activation and dissociation reactions possessing multiple wells and multiple products. We show that direct approximation of the rate coefficients via Chebyshev expansions yields reliable and accurate representations of their pressure and temperature dependences, which are superior to those from a Lidemann approach to fit the form factor representing the fall-off surface. The superiority of the method is demonstrated in a study of seven channels corresponding to four different reactions important in combustion chemistry over the ranges 300-3,000 K and 0.02-200 atm.
    Additional Material: 4 Tab.
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  • 389
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    AIChE Journal 43 (1997), S. 1377-1389 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Network models are an effective means of incorporating pore-scale heterogeneity into flow models of porous materials. The drawback to these models used to be the inability to obtain quantitative macroscopic parameters representing larger (experimental-scale) media. However, recently developed modeling techniques, combined with more widely available computational resources, make the simulation of macroscopic parameters from a network approach viable. A network model for the slow flow of an incompressible fluid in disordered packed beds is presented. Fundamental fluid mechanics equations are solved at the pore scale and then translated to macroscopic behaviour using a network approach. The results reproduce experimental permeabilities and show excellent quantitative fits to residence time distributions for mechanical dispersion in real beds. Simulations of the RTD are of special interest, because they are definitive links between pore-scale flow behavior and macroscopic responses.
    Additional Material: 11 Ill.
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  • 390
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997) 
    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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  • 391
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1662-1674 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Microwave thawing of materials, which melt over a finite temperature range, are analyzed using the effective heat capacity method. The state of the material, solid, liquid or mush is deduced from the equilibrium liquid volume fraction vs. temperature relationship for the substance, and the microwave power is calculated from Maxwell's equations. Using Galerkin finite elements, the microwave power, temperature and liquid volume fractions were obtained for microwave thawing of tylose slabs. Thawing progresses from the inside and/or outside depending on the slab thickness. For slabs ≥ 5 cm, thawing progresses predominantly from the surface of the sample. Resonances, during which the microwave power absorption is high, causes the 2-cm slab to thaw quicker than 1-cm slabs. A power law for the thawing time vs. sample thickness yields an exponent of 1.56 for microwave thawing and 2 for conventional thawing. To control the temperature rise in the liquid regions, simulations were carried out with an on-off control on the microwave power. On-off control results in greater power savings for thick samples.
    Additional Material: 15 Ill.
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  • 392
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    AIChE Journal 43 (1997), S. 1684-1690 
    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 study back-propagation, feed-forward neural networks are applied to estimate mass-transfer parameters in fast fluidized beds of fine solids. These networks are trained to predict mass-transfer rates using measurements of the sublimation rate of coarse naphthalene balls in fast fluidized beds of fine glass beads at several solid-to-gas mass flow rates within the relevant superficial gas-velocity range. When tested to predict the effective diffusivities from a coarse particle to the bulk of the fast bed of fine solids, trained neural networks calculated the Sherwood number with high accuracy. It is demonstrated that back-propagation, feed-forward neural networks provide a more accurate correlation for the mass-transfer coefficient compared to those obtained by the currently used heuristic models.
    Additional Material: 5 Ill.
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  • 393
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    AIChE Journal 43 (1997), S. 1700-1708 
    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 shear and compressive properties of aggregated alumina particles are determined as functions of volume fraction and the strength of the interparticle attraction. Over a range of volume fractions, yield stresses, τy, elastic moduli, the strain delimiting the extent of the linear elastic response, and compressive yield stress, Py, are well described by power-law functions of volume fraction, while the role of interparticle attractions can be accounted for by expressing these mechanical properties as (φ/φg - 1)n, where φg captures the strength of particle attractions and n the microstructure. The links between compressive and shear properties are well described by linear elastic models where the Py and τy are a function of Poisson's ratio which, for the suspensions investigated, has a value near 0.49.
    Additional Material: 9 Ill.
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  • 394
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    AIChE Journal 43 (1997), S. 1737-1750 
    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 systematic method is presented to synthesize reactive crystallization processes. It shows how to selectively crystallize a desired solid product(s) after a reaction step and how to use compound formation to effect separation of a mixture. The method is based on the generation of phase diagrams with liquid-phase reactions. Using transformed coordinates, systems with three or fewer degrees of freedom can be conveniently analyzed, regardless of the number of components and reactions. Features of the solid-liquid phase diagram that are relevant to process synthesis are identified. The method is illustrated with systems with multiple components, complex reactions, and multiple phases.
    Additional Material: 15 Ill.
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  • 395
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    AIChE Journal 43 (1997), S. 1813-1818 
    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 catalytic hydrogenation of alpha-methylstyrene to cumene is studied in a laboratory trickle-bed reactor operated at low liquid flow rates. Under this condition, wetting is not complete, vaporization of the liquid phase may occur, and reaction could proceed via liquid-solid and gas-solid catalysis, which increase the hydrogenation rate significantly. To determine and quantify the effect of the gas-solid catalyzed reaction, we propose the use of post-packing sections of increasing lengths. The inert bed acts as an absorber of the gas-phase-produced cumene. The liquid and gas effluent were monitored. Experimental global rates determined from liquid cumene concentrations varied with the post-packing length. A simple one-dimensional model developed shows that theoretical and experimental results agree well.
    Additional Material: 6 Ill.
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  • 396
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    AIChE Journal 43 (1997), S. 1988-1988 
    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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  • 397
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    AIChE Journal 43 (1997), S. 1964-1974 
    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 use of optical fibers in a fluorescence-detection scheme permits the accurate determination of the radial distribution of the transit time, the column efficiency, and the analyte concentration at the exit of a chromatographic axial-compression column (50 mmID). The results obtained demonstrate that the column is not homogeneous, but suggest a nearly cylindrical distribution of the packing density. The average velocity close to the column wall is 7% lower than along its axis and the HETP 25% higher. The lack of homogeneity of the column packing is another source of band broadening not taken into account in chromatography so far. It causes the apparent HETP derived from the conventional elution chromatogram recorded on the bulk eluent to be larger than the local HETP and the band profile to be unsymmetrical with a slight tail reminiscent of kinetic tailing.
    Additional Material: 9 Ill.
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  • 398
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    AIChE Journal 43 (1997), S. 1975-1988 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Hollow-fiber membrane processes with a constant external resistance having a constant or variable shell concentration resulting from an operational mode of cocurrent or countercurrent are studied. By solving numerically the continuity mass-conservation equation with the corresponding boundary conditions, the lumen laminar mass-transfer coefficients for both cases are correlated. The correlations greatly improve the calculating accuracy of the overall mass-transfer coefficient and can be used to obtain the lumen mixed-cup concentration by an algebraic equation substituting the partial differential equation. A separation factor m' is introduced to characterize the effect of the operational mode. Calculation results demonstrate that the lumen mass-transfer coefficient is independent of the real lumen and shell concentrations, but it is greatly influenced by m'. The countercurrent mode, compared to the cocurrent mode, provides not only a higher mean driving force, but a higher lumen mass-transfer coefficient. This conclusion is novel and valid for the tube-shell heat or mass-transfer processes and is supported by the experimental data in the literature and our gas membrane separation experiments.
    Additional Material: 9 Ill.
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  • 399
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    AIChE Journal 43 (1997), S. 1989-2001 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Sheet and film processes pose a challenging identification and control problem due to high complexity, poor conditioning, and limited input-output data. The interaction between model accuracy and closed-loop performance is explored for sheet and film processes using a model decomposition in terms of two static orthogonal matrices in series with a diagonal transfer-function matrix. It is shown that the accuracy of the diagonal elements of the transfer-function matrix directly specifies the closed-loop performance achievable by a model-based controller. This motivates the development of a combined identification and control procedure in which the controller is designed to be robust to model inaccuracies quantified during identification. The resulting controller is compared to an industrially accepted controller design method for two examples, including a simulated blown-film process. Based on the theoretical results and simulations, it was concluded that the poor performance often reported for existing industrial sheet and film process-control systems is likely due to signs of the model gains being incorrectly identified.
    Additional Material: 14 Ill.
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  • 400
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    AIChE Journal 43 (1997), S. 2021-2033 
    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 simultaneous control of composition and molecular weight of copolymers produced in semicontinuous emulsion polymerization is addressed. A first-principles model of emulsion copolymerization is used to produce optimal open-loop policies, which are then experimentally tested on the system methyl methacrylate/vinyl acetate. In contrast to earlier work in the control of semicontinuous emulsion copolymerization, the control problem addressed has multiple inputs and multiple outputs, and the experimental application is free of empirical correlations and performed on an unseeded system. Optimal open-loop policies are calculated efficiently by optimizing properties of the instantaneous polymer being formed. The experimental results confirm the feasibility of these techniques. A model-predictive control scheme, in which optimal policies are recomputed on-line to account for disturbances, is proposed. The scheme, which exploits the advantages of the efficient calculation of optimal policies, is tested by simulation showing good performance.
    Additional Material: 12 Ill.
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