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  • 1
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 422-433 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The memory integral based on convolution of the unit step response to loading a clean pellet with concentration history at the pellet surface is proposed for computations of mass transfer in adsorption process simulation. Although rate laws are widely used to describe diffusion and sorption in pellets for slow (Glueckauf, 1955) and moderate (Kim, 1989) rates of mass transfer, these models fail to describe mass transfer at short contact times because the concentration history experienced by the pellet is not accounted for. To facilitate memory integral computations, approximations to the unit step response to loading a clean pellet are derived based on a single moving finite element and by asymptotic matching in time. Numerical evaluation of the memory integral is demonstrated on simple cycles which show the merits of this approach.
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  • 2
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    AIChE Journal 39 (1993), S. 397-412 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The problem of bulk, transition and Knudsen regime diffusion in structures of freely overlapping fibers of various orientation distributions was numerically investigated, and the interrelation of the resulting effective diffusivities was examined. Fibers were randomly positioned and oriented in d = 1, 2, or 3 directions. A Monte Carlo simulation scheme was employed to determine the effective diffusivities from the mean-square displacement of random walkers traveling in the interior of the porous structure. The effective diffusivity was found to depend strongly on the orientational distribution of the fibers, porosity of the fibrous structures, and Knudsen number. The tortuosity factor decreased in general with increasing porosity, approaching at the limit of dilute beds the lower bound derived for each direction of diffusion from variational principles. The simulation results agreed well with experimental values of the bulk tortuosity of fibrous beds from the literature. It was also found that the reciprocal additivity or harmonic average effective diffusivity expression (Bosanquet formula), commonly used to estimate transition regime diffusivities from the values at the ordinary and Knudsen diffusion limits, provides an excellent approximation for the effective diffusivity of fibrous beds, except for that parallel to the fibers of a unidirectional structure.
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  • 3
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    AIChE Journal 39 (1993), S. 461-470 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The asymptotic behavior of fixed-point methods in the complex domain is studied. Both direct substitution and Newton's method exhibit stable periodic and aperiodic behavior from real- or complex-valued starting points. Moreover, multiple stable periodic orbits can exist for direct substitution. Traditional trust region (or dogleg) methods, on the other hand, often terminate at singular points, which correspond to nonzero-valued saddlepoints in the least-squares function that can be arbitrarily far from a solution. Furthermore, the basins of attraction of these singular points are usually dispersed throughout the basin boundaries in the complex domain, clearly illustrating that singular points (via the dogleg strategy) also attract either real- or complex-valued starting points.In light of this, an extension of the dogleg strategy to the complex domain, based on a simple norm-reducing, singular point perturbation, is proposed. This extended trust region method removes all forms of nonconvergent behavior and always terminates at a fixed point, even from critical point (worst-case) initial values. Many numerical results and geometric illustrations using chemical process simulation examples are presented.
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  • 4
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    AIChE Journal 39 (1993), S. 446-460 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Most of the advanced nonlinear control algorithms require a model of the system to be controlled. Unfortunately, most of the processes in the chemical industry are nonlinear, and fundamental models describing them are lacking. Thus there is a need for the identification and control of nonlinear systems through available inputoutput data. In this article, we briefly introduce the input-output model used (polynomial ARMA models), and analyze its stability and invertibility. This paves the way to the development of a nonlinear-model-predictive controller. Implementation issues such as modeling of disturbance, state and parameter estimation are discussed. The theory presented is illustrated through examples.
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  • 5
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    AIChE Journal 39 (1993), S. 471-492 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The separation of a binary mixture, using a third component having intermediate adsorptivity as desorbent, in a four section countercurrent adsorption separation unit is considered. A procedure for the optimal and robust design of the unit is developed in the frame of Equilibrium Theory, using a model where the adsorption equilibria are described through the constant selectivity stoichiometric model, while mass-transfer resistances and axial mixing are neglected.By requiring that the unit achieves complete separation, it is possible to identify a set of implicit constraints on the operating parameters, that is, the flow rate ratios in the four sections of the unit. From these constraints explicit bounds on the operating parameters are obtained, thus yielding a region in the operating parameters space, which can be drawn a priori in terms of the adsorption equilibrium constants and the feed composition.This result provides a very convenient tool to determine both optimal and robust operating conditions. The latter issue is addressed by first analyzing the various possible sources of disturbances, as well as their effect on the separation performance. Next, the criteria for the robust design of the unit are discussed. Finally, these theoretical findings are compared with a set of experimental results obtained in a six port simulated moving bed adsorption separation unit operated in the vapor phase.
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  • 6
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    AIChE Journal 39 (1993), S. 505-509 
    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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  • 7
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    AIChE Journal 39 (1993), S. 513-517 
    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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  • 8
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    AIChE Journal 39 (1993), S. 518-520 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 9
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    AIChE Journal 39 (1993), S. 510-512 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 10
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    AIChE Journal 39 (1993), S. 1716-1720 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Chabazite zeolites are used at Oak Ridge National Laboratory to decontaminate wastewaters containing 90Sr and 137Cs. Treatability studies show that chabazite can remove trace amounts of these nuclides from wastewaters containing much higher concentrations of calcium and magnesium. The design of ion-exchange columns for multicomponent systems requires a method for predicting multicomponent equilibria from binary, ternary and quaternary experiments, since the number of experiments required for an empirical equilibrium model is not generally feasible. Binary interaction parameters for the Wilson equation are used to predict solid-phase activity coefficients for the five-component system. The sum of squares of deviations between experimental and predicted solution concentrations for the data points available is calculated. The average deviation per data point for the five-component system is lower than for some of the ternary-and four-component data sets containing calcium or magnesium.
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  • 11
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    AIChE Journal 39 (1993), S. 1708-1715 
    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 limiting current technique was used to measure area-averaged mass-transfer coefficients for surfaces containing many small reactive areas arranged in various patterns. Partially masked platinum electrodes were fabricated using photolithography, and mass-transfer measurements were performed with a rotating disk apparatus. The average mass-transfer coefficient was sensitive to the fraction of the electrode area exposed (ε), declining from values near that for a fully exposed surface for ε = 0.5 to less than 1% of the fully exposed value for ε = 0.001. For any given ε, the mass-transfer coefficient declined with increased spacing between reactive sites. The results were relatively insensitive to details of the site distribution, such as whether the sites were arranged in regular arrays (square or hexagonal lattices) or distributed randomly over the surface. For all conditions studied, the mass-transfer coefficient greatly exceeded that predicted by conventional models which apply the stagnant film approximation to the fluid surrounding a representative active site. This finding is qualitatively consistent with recent computational results, which suggest that convective transport enhances mass transfer at partially active surfaces to an extent not accounted for by adjustments in the effective film thickness.
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  • 12
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    AIChE Journal 39 (1993), S. 1720-1720 
    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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  • 13
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    AIChE Journal 39 (1993), S. 1272-1280 
    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 instability analysis has been carried out to elucidate the unsteady flow conditions encountered in the typical circulating fluidized bed units in light of the conveyor-solids feeder interaction. The results successfully predict the critical velocity and the maximum solids circulation rates reported in the literature and explain the origin of such unstable conditions. Furthermore, the simulation, for the first time, reveals the importance of unit structure in improving the performance of circulating fluidized bed systems. Finally, the concept of a high-density circulating fluidized bed is proposed.
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  • 14
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    AIChE Journal 39 (1993), S. 1303-1321 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The product compositions in single-feed distillation columns can be specified only in certain regions of the composition space, which depend only on the pressure, feed, and vapor-liquid equilibrium for the mixture. In nonideal mixtures, even without azeotropes, the regions may allow unusual product distributions. For example, the distillate in a “direct split” is composed primarily of the lightest component. Intuition and experience with relatively ideal mixtures suggest that the next most plentiful component is the intermediate boiler. In nonideal mixtures, however, with or without azeotropes, the next most plentiful component may be the highestboiling species with only trace amounts of the intermediate boiler. For azeotropic mixtures, distillation boundaries may give rise to additional restrictions on the product compositions. We describe how simple distillation boundaries deform into continuous distillation boundaries and, in a limited number of cases, how the simple distillation boundaries can be crossed in continuous columns for certain ranges of the design variables. Unfortunately, such designs may be quite sensitive to model uncertainties or to disturbances in the parameters.
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  • 15
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    AIChE Journal 39 (1993), S. 1377-1388 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Deposition of wax on the wall of oil pipelines is often regarded as a problem since the tube diameter is reduced. Consequently, more power is needed to force the same amount of oil through the system. A mathematical model for quantitative prediction of wax deposition for each hydrocarbon component has been developed. Each component is characterized by weight fraction, heat of fusion, and melting point temperature. A model explains how a phase transition in the flow from liquid oil to waxy crystals may create a local density gradient and mass flux, which depends on the local temperature gradient. The model predicts that wax deposition can be considerably reduced even when the wall temperature is below the wax appearance point, provided the liquid/solid phase transition, expressed by the change in moles of liquid with temperature, is small at the wall temperature. Deposition as function of time has been obtained as a solution of differential equations derived from the principles of mass and energy conservation and the laws of diffusion.
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  • 16
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    AIChE Journal 39 (1993), S. 1411-1414 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 17
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    AIChE Journal 39 (1993), S. 1415-1419 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 18
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    AIChE Journal 39 (1993), S. 1389-1397 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Rigorous and approximate methods are compared for the simulation of CO2 absorption into aqueous alkanolamine mixtures of methyldiethanolamine and diethanolamine. In addition, data for the mixtures containing monoethanolamine and the simultaneous absorption of CO2 and H2S are presented. For the rigorous approach, the simplified eddy diffusivity theory is used to simulate the liquid-phase hydrodynamic characteristics. The approximation methods examined are the pseudo-first-order approximation, the interpolation approximation of Wellek et al. (1978), the algebraic combined flux (ACFLUX) approximation and the modified combined flux (MCFLUX) approximation. The latter approximation utilizes the reaction zone concept to determine the kinetic preference of the absorbing gas at the gas-liquid interface. Under the range of conditions studied, the MCFLUX approximation predicts very accurately the CO2 and H2S flux rates in mixed amine systems, as compared with the rigorous solution of the differential equations.
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    AIChE Journal 39 (1993), S. 1406-1410 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 20
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    AIChE Journal 39 (1993), S. 1420-1420 
    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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  • 21
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    AIChE Journal 39 (1993) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 22
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    AIChE Journal 39 (1993), S. 1431-1443 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A steady-state method recently proposed for measuring two-phase flow properties of a porous medium is supplemented by NMR imaging for measuring the saturation gradients which are allowed to persist in the specimen. The method relies on a strong capillary end effect which is assumed to be enforced by an outlet capillary pressure boundary condition, but direct verification of this has not hitherto been available. For constant flow rates, incremented stepwise, steady-state profiles of hydrocarbon saturation So are obtained which agree with predictions that they be monotonic, nonintersecting, and convex.Using D2O for the aqueous phase allows unambiguous detection of hydrocarbon by NMR, and imaging measurements of transverse relaxation time T2 were included in the protocol. T2 shows a dependence on So which is mild but not negligible for quantitative NMR imaging.
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  • 23
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    AIChE Journal 39 (1993), S. 935-945 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experiment has been made on ribbing induced on a film coated over a roll surface by a two-roll system: one roll rotated with a speed and the other fixed or rotated with relatively different speeds. The two rolls have the same diameters and are placed parallel with each other by keeping a gap. Test fluids are Newtonian (glycerin/water) and viscoelastic [polyacrylamide (Separan AP30)/glycerin/water] solutions. Wavelength and depth of ribbing are measured by a newly developed technique utilizing an image of a straight bar placed above the roll and reflected on the ribbing film surface. Nondimensionalized wavelength is correlated with capillary number for Newtonian liquids, but higher for dilute Separan solutions and lower for nondilute Separan solutions than for Newtonian liquids. The depth of ribbing increases for dilute Separan solutions with nearly the same value for nondilute Separan solutions as those for Newtonian liquid. This behavior observed for the ribbing seems to have some relation to the existence of a line of vortices that occurs visibly for nondilute Separan solutions in the entrance region of the gap between the rolls. Increase in the ratio of the velocities of two rolls has an effect of increasing both the wavelength and depth of ribbing for glycerine and nondilute Separan solutions, but it has the effect of decreasing them for dilute Separan solutions. Addition of Separan in glycerine solution promotes the generation of ribbing.A string spanned near over the gap to touch the surface of the liquid pool between the gap has the effect of eliminating the ribbing. This is successful in various combinations between the speeds of the two rolls and the diameters of the string.
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    AIChE Journal 39 (1993), S. 954-961 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Variations of perturbation chromatography were used to measure Henry's constants and equilibrium isotherms of various gases on silicalite. Three different adsorbent samples were analyzed (commercial powder and extruded pellets, and laboratory-synthesized crystals), and no discernable differences among the measured parameters were noted. Henry's constants for the linear alkanes were determined from isobaric and nonisobaric chromatography experiments. They were correlated successfully with temperature and the number of carbon atoms per adsorbate molecule. Isotherms were measured from concentration pulse or tracer/concentration pulse chromatography techniques. The Flory-Huggins version of the vacancy solution model was used to correlate pure gas isotherms and predict binary behavior successfully.
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    AIChE Journal 39 (1993), S. 962-974 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Micropore diffusion coefficients for infinitely-dilute methane, ethane, propane, n-butane, and isobutane in silicalite were measured via concentration-pulse chromatography. Two different samples of large laboratory-synthesized crystals were investigated. Analysis of van Deemter plots clearly indicated the presence of a significant micropore mass-transfer resistance for isobutane. Diffusion coefficients evaluated from these plots were consistent with results measured by the membrane technique. The linear alkane data differed completely in that the micropore masstransfer resistance for these adsorbates was very small, implying that the true diffusion coefficients were too large to be measured with this system. Thus, effective diffusion coefficients evaluated from these data represent a lower limit of the true values. Comparison of this limit with nuclear magnetic resonance data was favorable, since the latter are significantly larger in magnitude. Inconsistency was observed with diffusion coefficients obtained from other macroscopic techniques including the membrane method, zero-length and tracer-pulse chromatography, and some frequency response experiments.
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    AIChE Journal 39 (1993), S. 855-866 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A nonlinear model-based scheme is developed for product property control in industrial gas-phase polyethylene reactors. The controller regulates instantaneous melt index and density, and provides servocontrol during grade changeovers. Hydrogen and butene feed rates are manipulated to force the product properties onto desired trajectories. During grade changeovers, these trajectories are determined from off-line dynamic optimization studies. Optimal open-loop policies for reactor temperature, bleed stream flow, catalyst feed rate, and bed level are implemented as part of the changeover strategy.The nonlinear feedback controller design is based on global input/output linearization methods. Disturbances are estimated, and plant/model mismatch is removed using an extended Kalman filter. Simulations on a complex mechanistic model of the process reveal that the nonlinear controller performs well for both regulatory and servocontrol. An analogous linear IMC controller is inadequate for disturbance rejection at different operating conditions and for control during grade changeovers. The simplicity of the nonlinear control algorithm makes it an interesting candidate for industrial application. This single controller can be used to control the properties of many grades of polyethylene made in the reactor and to accomplish near optimal changeovers between these grades.
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    AIChE Journal 39 (1993), S. 885-893 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A simple fluid dynamic model is developed which predicts the thinning rate of a viscous film of liquid, in contact with the smooth interior surface of a long cylindrical tube, due to the shearing action of a turbulent flow of an immiscible fluid through the tube. Experiments indicate the degree to which the model provides an accurate means of predicting viscous film removal from the tube. Similar experiments performed with electrochemically roughened tubes elucidate the limitation of this cleaning process due to surface roughness. The observed limitation is consistent with an analysis based on numerical solutions of the equations for shear flow over a rough surface.
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    AIChE Journal 39 (1993), S. 867-875 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A continuous electrochemically modulated complexation (EMC) process was devised to extract and concentrate a class of heterocyclic nitrogen compounds. This design is composed of flow-through electrolysis cells for redox modulation and cycling of the complexing agent and hollow-fiber membrane modules for phase contacting. The extent of both extraction and concentration was found to depend mainly on the magnitude of the distribution coefficients for both steps. Experimental results and modeling of this continuous EMC process are reported, as well as potential applications for this process for other separations.
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    AIChE Journal 39 (1993), S. 1791-1798 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Adsorption rates and thermodynamic parameters were determined for the gasphase adsorption of n-alkanes and benzene derivatives on octadecylsilyl-silica gel (ODS) by chromatographic measurement and moment analysis. Thermodynamic characteristics of adsorption phenomena on ODS were similar to those on the surface. The contribution of intraparticle diffusion to mass-transport resistance was dominant in the ODS column, and the role of surface diffusion was significant for the intraparticle diffusion. The values of the surface diffusion coefficient were of the order of 10-5 cm2/s and could be estimated by assuming that the surface migration on ODS is a tracer diffusion of an adsorbate molecule in n-octadecane.
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    AIChE Journal 39 (1993), S. 1799-1809 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nonisothermal adsorption is studied by incorporating its mathematical description into a model consisting of the full two-dimensional Navier-Stokes equations and energy and species concentration equations to simulate the processes in fixed-bed industrial adsorbers/regenerators. The model partial-differential equations are solved numerically by using well-established computational fluid dynamics techniques. The equilibrium between gas and solid is considered nonlinear, which is described by Freundlich-type equations. The transport and adsorption of a compound from a solvent to and into an adsorbent are described by a two-step process: transport through the “film” to the outer surface of the particle and diffusion into the porous particle. The effect of fill resistance is discussed, as well as a two-equation turbulence model. Solutions obtained for a typical industrial adsorber/regenerator demonstrate the potential of this method. The computed results for various flow ratios and parameters in the Freundlich equations are shown to be physically plausible.
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    AIChE Journal 39 (1993), S. 1164-1177 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The direct oxidation of CH4 to H2 and CO in O2 and in air at high temperatures over alumina foam monoliths coated with high loadings of Pt and Rh has been simulated using a 19-elementary-step model of adsorption, desorption and surface reaction steps with reaction parameters from the literature or from fits to previous experiments. The surface reaction model for Pt is in good agreement with previously reported low-pressure(0.1 to 1 torr) reactor measurements of CH4 oxidation rates at temperatures from 600 to 1,500 K and of OH radical desorption during CH4 oxidation at 1,300 to 1,600 K over polycrystalline Pt foils. The model predictions for both catalysts are also consistent with product selectivities observed over monolithic catalysts in an atmospheric-pressure laboratory-scale reactor, and the differences between Pt and Rh can be explained by comparing individual reaction steps on these surfaces. Because of the good agreement between the model and both low-and atmospheric-pressure reactor simulations, a complete energy diagram for methane oxidation at low coverages is proposed. The model results show that under CH4rich conditions at high temperatures, H2 and CO are primary products of the direct oxidation of methane via a pyrolysis mechanism.
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  • 32
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    AIChE Journal 39 (1993), S. 1196-1209 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A model for a pilot-scale chemical vapor infiltration (CVI) reactor in which multiple substrates are densified simultaneously by carbon deposition from a pyrolyzing hydrocarbon is presented. Kinetic expressions and parameters and transport properties for carbon deposition from propylene determined from experimental studies and a single substrate CVI model are incorporated into the pilot reactor model. The two-dimensional transport equations for heat, mass and momentum transfer are solved for the entire reactor to simulate the effects of varied operating conditions on substrate densification throughout the reactor during the CVI process. Of the conditions simulated, the reactor temperature was found to have the most significant impact on both the uniformity of densification and the process time required. As the temperature increased, the uniformity of densification decreased and the time at which pore blockage at the outer surface occurred was shortened. Increasing the hydrocarbon feed concentration shortened the process time, but did not affect the final level of densification, while the feed rate only affected CVI at intermediate times. Comparison between experimental pilot reactor results and model predictions were satisfactory at short and long times, but agreement was less satisfactory at intermediate times.
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    AIChE Journal 39 (1993), S. 1186-1195 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Solid-state film ion exchange (Ag+-Na+) in glass substrates has been investigated for the fabrication of passive, integrated, optical waveguides. A new ion exchange mechanism is proposed which couples the oxidation of silver metal to silver oxide and the diffusion of silver ions into the glass substrate. At high electric fields and/or high temperatures, the growth rate of a silver oxide film limits the formation of mobile silver ions and constrains the diffusion of silver into the glass. This new mechanism is able to predict the dopant distribution profile under those conditions and under conditions where a constant surface concentration is appropriate (infinitely thick oxide film). It also explains the characteristics of the current vs. time curve measured during the ion exchange process. The formation and growth of the silver oxide film were confirmed by X-ray photoelectron spectroscopy and X-ray diffraction analysis.
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    AIChE Journal 39 (1993) 
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    Keywords: Chemistry ; Chemical Engineering
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  • 35
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    AIChE Journal 39 (1993), S. 1281-1291 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mechanistic model of slug flow based on a set of mass and momentum conservation equations and a number of empirical closure relations is presented. It is then shown that a simplified version of the model, which physically corresponds to the flow of long liquid slugs(long slug model, LSM), can be immediately derived from the general model. The LSM is much simpler than the general model; at the same time, the predictions obtained in the two cases are very similar, when the comparison is limited to the computation of the pressure gradient and the mean liquid holdup. The LSM successfully correlates a large set of experimental measurements relative to three pipe diameters(18, 50 and 90 mm), four inclinations (0°, ±3°, 0.3°), and two pipe lengths(17 and 34 m).
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    AIChE Journal 39 (1993), S. 1322-1329 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: We present a theoretical study of the adsorption kinetics of particles with a continuous distribution of sizes. If the particles interact with short-ranged forces, the diminishing rate of adsorption with increasing surface coverage can be attributed to a geometrical blocking effect of the preadsorbed particles. We exploit the fact that at low coverages the blocking effects result from isolated adsorbed particles to develop an analytic description of the adsorption kinetics using a moment expansion approach. We evaluate the time-dependent surface coverage, density and the average size of the adsorbed particles and compare these quantities with those of the bulk phase. The effect of desorption is studied by introducing a size-independent desorption constant, and the corresponding adsorption equilibria properties, which are valid at low coverages, are derived. Simulation results for irreversible adsorption are obtained and compared with the theoretical predictions.
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    AIChE Journal 39 (1993), S. 1938-1953 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Control structure (strategy) selection consists of the selection and pairing of manipulated and measured variables. This article outlines a procedure that uses such tools as the existence of right half plane (RHP) transmission zeros, the relative gain array, the performance relative gain array, and the closed-loop disturbance gain. The regulatory control system for the fluid catalytic cracking process is used as an example. Several authors found the Kurihara control structure to be preferable to the conventional control structure. The reason is that RHP transmission zeros limit the achievable bandwidth for the conventional control structure. Two other control structures, however, have better controllability characteristics than both the conventional and the Kurihara control structures. The sensitivity of the measurement selection and variable pairing with respect to changes in the operating point and parametric uncertainty is examined, as well as the general objectives of the regulatory control level and its interaction with the higher levels in the control hierarchy.
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    AIChE Journal 39 (1993), S. 1954-1965 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Sufficient conditions for robust closed-loop stability of a class of dynamic matrix control (DMC) systems are presented. The l1-norm is used in the objective function of the on-line optimization, thus resulting in a linear programming problem. The ideas of this work, however, are expandable to other DMC-type controllers. The keys to the stability conditions are: to use an end-condition in the moving horizon on-line optimization; to have coefficients of the move suppression term in the objective function of the on-line optimization satisfy certain inequalities; and to express the uncertainty as deviations in the unit pulse response coefficients of the nominal plant. These deviations and disturbances must also satisfy certain inequalities.An off-line tuning procedure for robust stability and performance of a class of DMC controllers is also included, which determines an optimal moving horizon length and optimal values for coefficients of the move suppression term. The applicability of our approach is elucidated through numerical simulations.
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    AIChE Journal 39 (1993), S. 1976-1984 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: We report experimental data showing the effect of temperature on polymer partitioning in the dextran (DEX500)-polyethylene glycol (PEG8000)-water system. Increasing temperature increases the concentration of PEG in the top phase and decreases the concentration of DEX in the bottom phase. A solution thermodynamic model based on local compositions with temperature-dependent parameters correlates the experimental data well, and an efficient Gibbs-free energy minimization algorithm for phase equilibrium calculations is described. The partial molar enthalpies and entropies of each of the solutes, calculated with the model, are negative and decrease in magnitude as temperature increases.
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    AIChE Journal 39 (1993), S. 1966-1975 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two cationic, copper metal complexes with different ligands were synthesized: ethylenediamine (en) [Cu(C2N8N2) (ClO4)2] and diethanolamine (Deta) {[Cu-C8H21N2O4]ClO4}. These complexes were mounted on Cab-O-Sil using nonaqueous impregnation techniques, and the loadings were determined at which multilayers formed. These samples were analyzed for copper, carbon, nitrogen and hydrogen content to determine if ligand dissociation occurred during the impregnation. Samples were decomposed in a thermal gravimetric apparatus to determine the kinetics of the thermolysis reaction in air, and the evolved gases were analyzed by gas chromatograph-mass spectrometry to determine the products of the thermolysis reaction. The results of these and earlier studies are summarized in a model that describes the effects of molecular structure upon complex-support interactions. Complexes with the ability to form hydrogen bond interactions between the ligand and the support form strong interactions with the surface of silica, whereas complexes without such hydrogen bond interactions are only weakly attracted to the silica surface. Strong interactions with the surface may also arise as a result of ligand dissociation and direct interaction of the metal ion with the surface oxygens. The charge on the complex and its shape play less important roles in determining the affinity of the metal complex with the silica.
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    AIChE Journal 39 (1993), S. 127-139 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Polymer microspheres and fibers are formed with a versatile new process, precipitation with a compressed fluid antisolvent. By spraying a 1 wt. % polystyrene in toluene solution into CO2 through a 100-μm nozzle, microspheres are formed with diameters from 0.1 to 20 μm as the CO2 density decreases from 0.86 to 0.13 g/cm3. The uniform submicron spheres produced at high CO2 density are due in part to the rapid atomization produced by the large intertial and low interfacial forces. Fibers, with and without microporosity, are obtained at higher polymer concentrations where viscous forces stabilize the jet. The effect of CO2 density and temperature on the size, morphology and porosity of the resulting polymeric materials is explained in terms of the phase behavior, spray characteristics, and the depression in the glass transition temperature.
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    AIChE Journal 39 (1993), S. 140-148 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Slit devolatilization of polymers has been considered in a recent work by Maffettone et al. (1991), who have presented a successful model for single slit devolatilization. In this article, the stability of operation of a realistic multislit process is considered. It is shown that the flow rate per slit which can be stably operated may be significantly less than the optimal one for single slit operation. Stability improves as the concentration of volatiles in the feed solution decreases. The non-Newtonian character of the feed solution at high shear rates is discussed in qualitative terms.
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    AIChE Journal 39 (1993), S. 149-162 
    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 nonintrusive technique for the in-situ measurement of interfacial pH and current efficiency has been developed. A ring electrode, operated potentiometrically at opencircuit, is used to measure the pH change at a rotating disk electrode. The technique takes advantage of the well-characterized hydrodynamics at the rotating disk electrode and has the added advantage that the pH probe, the ring electrode, is not interfering with the flow field and the current distribution on the disk. To determine the pH at the disk electrode by measuring the potential of the ring, the radial transport of hydronium ions across the insulating gap and on the ring is analyzed taking into account the effect of homogeneous dissociation reactions of water and metal-hydroxide ion complexes. Shifts in the ring potential caused by hydrogen super-saturation and ohmic drop are also evaluated. A platinized ring electrode in a hydrogensaturated electrolyte is shown to provide a stable and reproducible hydrogen ion sensor with a Nernstian response to the changes in the bulk pH. Performance of the ring is evaluated by generating hydrogen at the disk electrode from a dilute acid solution, in the absence of other electrochemical reactions. The technique is then applied to determine the interfacial pH of nickel, iron and nickel-iron alloy electrodeposition with concurrent hydrogen evolution. This method was also used to measure the current efficiency of nickel electrodeposition in a fast, nonintrusive and in-situ manner.
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    AIChE Journal 39 (1993) 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 193-196 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 215-223 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A simple statistical-mechanical theory, known as the random-phase approximation, is applied to study liquid-liquid phase separations in solutions of globular proteins. Phase separation may be induced by addition of nonionic polymer or/and ordinary electrolytes. In this analysis, the osmotic-attraction mechanism, whereby the depletion of “solvent” particles between two proteins causes an attractive force, is primarily responsible for phase separation. For one-component models of protein solutions, the theory yields simple algebraic expressions for the equation of state and for the chemical potential of the protein. This analytical theory describes the observed solubility behavior of proteins, including the effect of protein and polymer size, protein charge and concentration, and concentration of simple electrolytes.
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    AIChE Journal 39 (1993), S. 178-187 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: 2-Chlorophenol (2CP) was oxidized in near-critical and supercritical water in a high-pressure plug-flow reactor. The global kinetics for 2CP disappearance were described by a rate law that was 0.88±0.06 order in 2CP, 0.41±0.12 order in O2, and 0.34±0.17 order in water. The activation energy was 11.0±3.8 kcal/mol, and the Arrhenius pre-exponential factor was 102.0±1.2 M-0.63 S-1. The uncertainties represent 95% confidence intervals. The products of 2CP oxidation included CO, CO2, HCl, other chlorophenols, chlorohydroxybenzaldehydes, dichlorophenoxyphenols, dichlorobiphenols, and chlorinated dibenzodioxins and dibenzofuran. The molar yields of the organic products were determined for a set of experiments at 380°C and 278 atm. The most abundant products were 2CP dimers such as dichlorophenoxyphenols and dichlorobiphenols, and the highest yield observed for any individual product was 0.6%. Although the yields of these products were low, their selectivities were high. For example, at 3.6 s, the shortest residence time studied under these conditions, about 50% of the carbon in the 2CP that reacted appeared in 2CP dimers, 18% appeared as CO2, and the balance (32%) was presumably in single-ring and ring-opening products. A reaction pathway analysis using the Delplot methodology revealed that the evolution of products from 2CP oxidation in supercritical water was consistent with a reaction network comprising two parallel primary reactions. One primary reaction path led to dichlorophenoxyphenols and dichlorobiphenols whereas the second primary reaction led to single-ring and ring-opening products. The 2CP dimers were convereted to single-ring and ring-opening products, which were, in turn, ultimately oxidized to CO2.
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    AIChE Journal 39 (1993), S. 434-445 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Modeling of reverse osmosis in the presence of strong solute-membrane affinity has always been a challenge due to the complexity of the solute-solvent-membrane interactions and the resultant effect on membrane performance. Most transport models, including all models treating membranes as nonporous and those based on irreversible thermodynamics, are unable to describe or to predict all of the phenomena associated with this case. Recently, the modified surface force-pore flow model has been derived and used to describe the performance of reverse osmosis membranes for solutes which are rejected from the membrane. In the present work, this model is extended to a more general form which can describe the solute-membrane affinity case. For illustration, the extended model, with five adjustable parameters, is used to describe the performance for cellulose acetate membranes and dilute aqueous solutions of toluene, cumene, and p-chlorophenol (data from literature). The model is reasonably consistent with the data. Simulation results of the extended model are also shown.
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    AIChE Journal 39 (1993), S. 1563-1568 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 1569-1573 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    AIChE Journal 39 (1993), S. 1574-1576 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 1577-1577 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1581-1591 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Lagrangian statistics are explored as a means of describing the transport of solids in a turbulently flowing liquid. The essential feature of the approach is to represent the concentration field as resulting from a distribution of sources of particles. It is argued that this provides a better framework to understand the physics than the Eulerian analysis currently being used. Fully developed concentration fields are calculated, using the assumptions of homogeneous turbulence and plug flow. It is found that the configuration of solids and the suspended load depend primarily on the ratio of the settling velocity to the friction velocity, which is a measure of the relative importance of turbulence and of settling in depositing particles. The analysis emphasizes the need for a better understanding of the mechanism and the rate of entrainment of particles into a turbulently flowing liquid.
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    AIChE Journal 39 (1993), S. 1592-1602 
    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 velocity contour profiles within Dean vortices produced by flowing water in a solid-walled curved tube are quantitatively measured. Magnetic resonance flow imaging using flow encoding with spin warp imaging is used in two and three dimensions to obtain these velocities. These experimental measurements are then compared with simulations obtained from solutions of the Navier-Stokes and continuity equations for three axial flow rates. Numerical solutions were obtained with a finite volume method for curved tube Poiseuille flow.
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    AIChE Journal 39 (1993), S. 1603-1610 
    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 mixing length model describes the recently observed (Bilger et al., 1991) effect of chemical reactions on turbulent diffusivities. From this viewpoint, the coupling between microscale reactions and macroscale mixing occurs because the reaction rate is a quasitransferable property which causes more reaction in fluctuating fluid lumps leaving regions of high rate than low rate. The net effect, which raises or lowers reactant diffusivities, depends on a characteristic macromixing time and the rate at which the mean reaction rate changes with mean concentration: \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{{\rm \varepsilon}_A}}{{\rm \varepsilon}} = 1 - \tau _M \frac{{d\bar r_A}}{{d\bar C_A}} $$\end{document}The model shows correct qualitative behavior and appears to agree quantitatively with much of the existing data. It adds an apparent flux, ετM(drA/dy), to the convective diffusion equations which can enhance or hinder the normal turbulent fluxes, but is likely to have little effect on the mean concentration field.
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    AIChE Journal 39 (1993), S. 1611-1620 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An original technique for simultaneous measurements of concentration and velocity in a turbulent liquid flow with and without a chemical reaction is developed by combining a two-component He-Ne laser Doppler velocimeter with a Ar+ laserinduced fluorescence technique. The mass flux and eddy diffusivity of mass are estimated from the simultaneous measurements of concentration and velocity in a liquid shear-free mixing layer downstream of a turbulence grid. The results show that the present measuring technique enables us to simultaneously measure velocity and concentration with high resolutions and that the approximation of the mean gradient diffusion causes about 10% error in estimating the mass flux in a reacting liquid flow.
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    AIChE Journal 39 (1993), S. 1621-1627 
    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 dispersionless, adsorption equilibrium, plug-flow model of a countercurrent moving-bed chromatographic separator operating at steady state is investigated. The flux of the constituents of a binary mixture is examined via concentration-phase plane plots, which reveal a complex behavior depending on a parameter ó, the ratio of solid- and fluid-phase flow of the mobile phase. When the model is modified by incorporating finite mass-transfer rates, axial concentration profiles exhibit behavior that is characteristic of experimental observations, rather than the predictions of the ideal model. Numerical simulations with the finite mass-transfer model reveal an optimum operating condition.
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    AIChE Journal 39 (1993), S. 1628-1640 
    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 heterogeneous macropore, surface and micropore diffusion model recently proposed by Hu et al. (1993) for single-component systems is exiended to multicomponent systems in the description of sorption kinetics of gaseous adsorbates in bidispersed (macropore and micropore diffusions), heterogeneous microporous particles. This model describes sorption of gaseous adsorbates with allowance for the energy distribution of adsorption site for both equilibrium and diffusion of the adsorbed species. A uniform distribution is used to describe this energy distribution, and the cumulative energy distribution function is assumed the same for all species in the analysis of multicomponent mixtures. Extensive experimental data of ethane and propane in Ajax activated carbon are collected to study the effects of energy distribution on the binary adsorption, desorption, and displacement dynamics.
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    AIChE Journal 39 (1993), S. 1641-1653 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Measurements of temperatures (secondary outputs) and flows (inputs) are used to estimate product compositions (outputs) in a distillation column. The problem is characterized by strong collinearity (correlation) between temperature measurements and an ill-conditioned model from inputs to outputs. In a linear study, three estimator methods, the Kalman-Bucy filter, Brosilow's inferential estimator, and principal component regression (PCR), are tested for performance with μ-analysis. One can achieve remarkably good control performance with the static PCR estimator, which is almost as good as the dynamic Kalman filter. The quality of the estimate for these two estimators is improved by additional temperature measurements, although the improvement is only minor for more than about five measurements. On the other hand, the performance of the Brosilow inferential estimator may not improve by adding measurements due to sensitivity to modeling errors. For all estimators, the use of flow (input) measurements does not improve the estimator performance and does in fact damage the performance if a static estimator is used.
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    AIChE Journal 39 (1993), S. 1654-1667 
    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 of nonhlinear static and dynamic process modeling via recurrent neural networks (RNNs) is studied. An RNN model is a set of coupled nonlinear ordinary differential equations in continuous time domain with nonlinear dynamic node characteristics as well as both feedforward and feedback connections. For such networks, each physical input to a system corresponds to exactly one input to the network. The system's dynamics are captured by the internal structure of the network. The structure of RNN models may be more natural and attractive than that of feedforward neural network models, but computation time for training is longer. Our simulation results show that RNNs can learn both steady-state relationships and process dynamics of continuous and batch, single-input/single-output and multiinput/multioutput systems in a simple and direct manner. Training of RNNs shows only small degradation in the presence of noise in the training data. Thus, RNNs constitute a feasible alternative to layered feedforward back propagation neural networks in steady-state and dynamic process modeling and model-based control.
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    AIChE Journal 39 (1993), S. 1680-1686 
    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 pseudohomogeneous model is used to analyze the steady state of a sharp reaction front in a porous medium. The reaction rate is described by the flame sheet approximation, and an asymptotic matching analysis is used to determine the temperature, conversion and position of the reaction front. Both adiabatic and nonadiabatic operations are considered, and the effect of radiation is included in the adiabatic case. The results show that there exists a maximum molar flux before blowout occurs. The critical molar flux is decreased by higher activation energies, but it is increased by higher rate constants and flame temperatures. Radiation further stabilizes the flame against blowout. Expressions are provided for the flame temperature, reactant conversion and the conditions when blowout occur. It is also shown that under certain conditions the front has two steady-state positions.
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    AIChE Journal 39 (1993), S. 1668-1679 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Parametric sensitivity of a two-dimensional pulverized-fuel (PF) combustion model is studied extensively for the effect of parametric uncertainty on model predictions. Results show that error in coal devolatilization/oxidation parameters has the dominant effect on predicted burnout, NOx formation, local gas temperature, and coal-gas mixture fraction. Uncertainty in the turbulent particle dispersion parameters appears to have a secondary effect, while error in the particle-gas radiation parameters has little impact on model predictions. Regions of the computational domain exhibiting sensitivity to specific parameters are identified. Specific parameter sensitivity implies the relative importance of various mechanisms in the overall process. Turbulent particle dispersion seems to be important early in the reactor with kinetic processes dominating at and following the predicted ignition point. Radiation appears to be of minor importance. These results indicate the need for a better method of predicting the overall volatiles yield and further understanding of the devolatilization/oxidation mechanism and its role in the overall PF combustion process. The study provides fundamental direction for future comprehensive model development and focuses on experimental work to better quantify critical input parameters.
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    AIChE Journal 39 (1993), S. 1697-1707 
    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 bulk foams, the dependence of bubble size on time can be deduced from a hypothesis of statistical self-similarity and the scaling characteristic of the volume change rate of a foam bubble. If this rate, \documentclass{article}\pagestyle{empty}\begin{document}$ {\dot v} $\end{document}, scales as the mean bubble volume v to the power α, the total surface area of the foam decreases as an inverse of time to the power 1/[3 (1 - α)]. Coarsening of polyhedral foam scales with α = 5/6, when molecular diffusion limits gas transport across lamellae and liquid drainage through Plateau borders limits lamella thinning. Excess liquid is released by disappearing small bubbles and flows into the lamellae and Plateau borders of growing large bubbles. If none of this liquid accumulates in the foam, coarsening is exponential and α = 1. When resistance to mass transfer at the lamella surfaces is the rate-limiting step, polyhedral foam coarsens with α = 1/3. Coarsening of slowly draining, spherical-bubble foam scales with α = 0. The theory is compared with nine measurements of the total surface area of polyhedral and spherical-bubble foams pregenerated from aqueous solutions of sodium lauryl sulfate, hexadecyltrimethylammonium bromide, alpha-olefin sulfonate with alkyl chain lengths from C14 to C16, and two shaving creams. The theory also proves that the collapse of a two-dimensional, polygonal foam is self-similar and scales with α = l. In all cases, our theory agrees well with experiment and numerical calculations.
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    AIChE Journal 39 (1993), S. 1687-1696 
    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 combined-conjugated heat-transfer and fluid-flow analysis is presented for coating fibers by CVD in a vertical cylindrical quartz reactor. The numerical model focuses on radiation and natural convection. Three case studies are performed, and the wall temperature predictions are compared to experimental measurements. In the first case, the flowing gas is hydrogen, and conduction is more important than both radiation and convection, in which case measured and predicted wall temperatures agree excellently. In the second, hydrogen is replaced by argon, thus making radiation heat transfer more important than the previous situation. Three radiation models with increasing degrees of sophistication are compared: an approximate nongray model (no wavelength dependence of emissivity), an approximate semigray model, and a rigorous semigray model with view factor calculations. Comparison with experiments suggest that a semigray radiative analysis is needed for correct determination of wall temperatures. The third involves argon at a lower flow rate, where natural convection effects are more pronounced. Checking the validity of the Boussinesq approximation by incorporating the explicit dependence of density on temperature in the model shows a slight difference between the velocity fields predicted using the Boussinesq approximation and those obtained using the explicit dependence of density on temperature. However, there is negligible difference between the temperature fields predicted in the two cases.
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    AIChE Journal 39 (1993), S. 653-662 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This article discusses the effect of boiling inert hydrocarbon solvent on the model second-order transesterification reaction of ethylene/vinyl acetate copolymer with 3-phenyl 1-propanol. In the presence of boiling, the overall reaction rate increases substantially due to mass-transfer effects in the proximity of the vapor-liquid interface. The present experiments and theory indicate that during the lifetime of a bubble in the boiling medium, the concentrations of reactants and the catalyst increase significantly near the bubble surface due to the rapid diffusion of the inert solvent. After the bubble rupture, the concentration differences persist and continue affecting the chemical reaction rate. The combination of these effects is responsible for the apparent increase in the overall reactivity.
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    AIChE Journal 39 (1993), S. 1135-1145 
    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 work, the separation of carbon dioxide from methane by reactive liquid membranes consisting of the secondary amines, diethanolamine, and diisopropanolamine in polyethylene glycol with an average molecular weight of 400 was studied. A mathematical model was developed to describe the transport process. This model employs the zwitterion mechanism for the CO2 amine reaction kinetics. Membrane flux experiments utilizing a flat plate device were carried out to verify the model predictions. It was found that large permeabilities and separations were achieved for low CO2 feed concentrations. The results also show that DEA based solutions give better separation than DIPA based solutions.
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    AIChE Journal 39 (1993), S. 1-1 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 27-36 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: There is as yet no theoretically sound and empirically proven procedure that is fully reliable for the design of thickeners. From a logical standpoint, a sound procedure is one correctly deduced from valid premises or assumptions. As noted in Fitch's earlier work(979), there is no reason to believe that existing mathematical models are based on uniformly valid assumptions. There is also much reason to believe that they are not. Therefore existing mathematical models or “theories” of thickening are analyzed for mathematical consistency, scientific credibility, and relevance to chemical engineering. Domains in which the models are useful approximations of reality and thus are relevant to chemical engineering practice are identified. Emendations or alternatives are suggested to bring the models more nearly into conformity with empirical results. Design procedures are suggested that, although involving assumptions that cannot be uniformly valid, would seem more reasonable than existing ones.
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    AIChE Journal 39 (1993), S. 1329-1329 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 1335-1341 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Equations introduced here identify measurement biases and process leaks, when gross errors exist in measured process variables and the variance-covariance matrix of the measurements, Σ, is unknown. Σ is estimated by the sample variance, S, using process data.For an unknown Σ, the global test statistic is the well-known Hotelling T2 statistic. Its power function has a noncentral F-distribution. For component tests used for specific identification of measurement biases and nodal leaks, two tests are presented with Σ unknown. The first test is independent of the number of component tests, k, and is given by a statistic with an F-distribution. The second test depends on k and has a student t-distribution. The power functions for both component tests are provided. Process examples and a Monte Carlo simulation study presented demonstrate the use and performance of these statistical equations in identifying biases and process leaks.
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    AIChE Journal 39 (1993), S. 1363-1369 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A systematic formulation of multicomponent/multiphase phase equilibria as a linear algebra problem in the fugacities, mole fractions, partial molar volumes, and partial molar enthalpies is given. The algorithm takes advantage of the Gibbs-Duhem relationships for each phase and a modified Gaussian elimination technique to reduce the system of equations. These algorithmic steps allow current symbolic manipulation packages to generate useful partial derivative relationships in terms of measurable thermodynamic quantities. Features of the algorithm are demonstrated by applying a computer implementation of the method to a simple two-phase/two-component system and to the more complicated examples of a two-phase/three-component supercritical fluid chromatography experiment and a mass-conserving closed system.
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    AIChE Journal 39 (1993), S. 82-88 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This article presents an approach to fault diagnosis of chemical processes at steadystate operation by using artificial neural networks. The conventional back-propagation network is enhanced by adding a number of functional units to the input layer. This technique considerably extends a network's capability for representing complex nonlinear relations and makes it possible to simultaneously diagnose multiple faults and their corresponding levels in a chemical process. A simulation study of a heptane-to-toluene process at steady-state operation shows successful results for the proposed approach.
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    AIChE Journal 39 (1993), S. 99-110 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Porous particles of two commercially available ZnO sorbents differing in porosity, surface area, and pore-size distribution were reacted with H2S at 500 and 600°C in a fixed-bed reactor. Concentration breakthrough curves were determined by analyzing the effluent of the reactor using a gas chromotograph equipped with thermal conductivity and flame photometric detectors. The pore structure of samples collected from different positions in the reactor was analyzed by mercury porosimetry and gas adsorption to determine the variation of the average structural properties of the sorbent with the length of the reactor. The obtained experimental data were used to validate a fixed-bed desulfurization model, which employs detailed submodels for diffusion, reaction, and structure evolution in the porous sorbent particles. With the various parameters appearing in the submodels determined from independent thermogravimetric reactivity evolution experiments, the fixed-bed desulfurization model was found to be capable of providing an excellent description of the behavior of the desulfurization sorbents in a fixed-bed reactor.
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    AIChE Journal 39 (1993), S. 89-98 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The occurrence of instabilities in chemically reacting systems, resulting in unsteady and spatially inhomogeneous reaction rates, is a widespread phenomenon. In this article, we use nonlinear signal processing techniques to extract a simple, but accurate, dynamic model from experimental data of a system with spatiotemporal variations. The approach consists of a combination of two steps. The proper orthogonal decomposition [POD or Karhunen-Loève (KL) expansion] allows us to determine active degrees of freedom (important spatial structures) of the system. Projection onto these “modes” reduces the data to a small number of time series. Processing these time series through an artificial neural network (ANN) results in a low-dimensional, nonlinear dynamic model with almost quantitative predictive capabilities.This approach is demonstrated using spatiotemporal data from CO oxidation on a Pt (110) crystal surface. In this special case, the dynamics of the two-dimensional reaction profile can be successfully described by four modes; the ANN-based model not only correctly predicts the spatiotemporal short-term behavior, but also accurately captures the long-term dynamics (the attractor). While this approach does not substitute for fundamental modeling, it provides a systematic framework for processing experimental data from a wide variety of spatiotemporally varying reaction engineering processes.
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    AIChE Journal 39 (1993), S. 189-192 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 163-177 
    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 most popular in vitro assay currently used to characterize cell traction forces exerted on extracellular matrix (ECM) fibers is the fibroblast-populated collagen lattice (FPCL) assay. The compaction of a disk of cell-populated collagen gel, in terms of rate or extent of diameter reduction, is typically reported as the measure of cell traction. This measure, however, depends on assay properties incidental to the intrinsic traction, such as the initial cell concentration, the initial collagen concentration, and the geometry of the gel. Thus, there is a clear need to identify and measure an objective index of cell traction. Here, we propose as such an index a traction parameter (reflective of the cell-fiber mechanical interaction) defined in a continuum theory in which the interactive processes of cell motility and ECM deformation are modeled by expressions for cell and ECM conservation coupled to the mechanical force balance for the cell-ECM composite. The equations are formulated and solved for our adaptation of the FPCL assay in which cells are initially dispersed in a collagen gel microsphere, conferring several experimental and theoretical advantages over the popular disk geometry. The solution of the nonlinear system of partial differential equations (parameterized on the traction parameter) is then compared to compaction data for the fibroblast-populated collagen microspheres (FPCM). We show that the model predictions are consistent with the data when the initial cell concentration and the initial FPCM diameter are varied. In Part 2, we show how these results, along with the determination of the growth parameters of the cells and the viscoelastic parameters of the gel, have allowed us to estimate the magnitude of the traction parameter, which is a direct measure of the traction exerted by fibroblasts in a physiologically relevant collagen gel.
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    AIChE Journal 39 (1993), S. 197-206 
    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 fractionation method for fine-particle suspensions using resonant ultrasonic fields coordinated with bidirectional fluid flow fields is described. The basis for the separation is differences in the speed of response of particles to the imposition of a resonant acoustic field. As such, the method is sensitive to the particle size and the acoustic contrast between the solid particles and their suspending fluid. Both batch and continuous fractionation processes can be developed from a two-step acoustic-flow cycle. An analytical model was constructed from equations that describe the trajectories of particles as they respond to the acoustic and flow fields. Model predictions indicate how the fractionation can be controlled through choice of cycle parameters. The method was implemented experimentally. Results for the fractionation of 325-mesh polystyrene spheres indicate that sharp fractionations can be achieved. The experimental results are generally in agreement with the model predictions.
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    AIChE Journal 39 (1993), S. 207-214 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Rheological behavior of moderately concentrated (up to 35 vol. %) suspensions or slurries prepared with non-Newtonian carrier fluids is investigated. Extensive experimental data on the Poiseuille slit flow of suspensions of sand in Hydroxypropyl Guar (HPG) solutions are presented. Flow data are gathered by pumping various non-Newtonian slurries into a unique, 8 ft (2.4 m) tall vertical apparatus, with great care taken to calibrate the instrument and to avoid settling difficulties. Investigated are the effects of polymer concentration, solids concentration, test temperature, and shear rate on the rheological properties of slurries. The rheological behavior of HPG solutions and HPG suspensions is characterized by a pseudoplastic power law non-Newtonian fluid model over a shear rate range of 30 to 500 s-1. The correlations for predicting the relative slurry viscosity for HPG fluids are presented. Substantial increase in viscosity of these non-Newtonian fluids is observed, and they are found to be a strong function of polymer concentration, shear rate, test temperature, and particle concentration. Results of this investigation are also compared with those available for Newtonian and non-Newtonian suspensions.
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    AIChE Journal 39 (1993), S. 235-248 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The addition of cosolvents to supercritical fluid (SCF) solvents can have large effects on solubilities, giving engineers the ability to tailor loadings and selectivities of solutes for difficult separations. It is necessary to have a better understanding of the special intermolecular interactions that occur in SCF solutions to predict the effects of cosolvents. We use a SCF chromatographic technique to acquire a database of cosolvent effects for a variety of cosolvents and solutes; examination of the cosolvent effects shows evidence of hydrogen bonding, charge transfer complex formation, and dipole-dipole coupling between solute and cosolvent molecules. SCF solvents, carbon dioxide, ethane, and fluoroform, are compared, and then the use of the chromatograph to measure solubilities is discussed.
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    AIChE Journal 39 (1993), S. 1455-1464 
    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 companion article (Chen and Hu, 1993a) discussed a statistical theory that for a system consisting of two closed subsystems, the residence time density (RTD) functions of the two subsystems will be statistically independent, if a two-dimensional perfect mixing exists at the subsystem boundary. In this case, the overall RTD function is related to that for individual subsystems through the convolution integral. This theory has been validated experimentally using two die-screw combinations.Based on this theory, a predictive RTD model for an intermeshing counterrotating twin-screw extruder has been developed. The screw in the longitudincl direction has been treated as C-chambers in series. The overall RTD of leakage flows has been calculated from the RTDs of these individual chambers and then converted into the RTD of the extruder. The predicted RTD has been tested against experimental results with success.
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    AIChE Journal 39 (1993), S. 1444-1454 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetics of hydrogen absorption and desorption in LaNi4.8Al0.2,LaNi4.9Al0.1 and LaNi5, suspended in cyclohexane and LaNi5 in ethanol have been investigated. The absorption process can be described in terms of mass transfer and reaction resistances in series. The rate-limiting steps for this process are dissolution of hydrogen in the solvent and the reaction of hydrogen with the metal alloy. Over a broad range of hydrogen loadings, the reaction of hydrogen with the metal follows the rate equation:\documentclass{article}\pagestyle{empty}\begin{document}$$ R_{{\rm abs}} = k_a a_s \left({C_{{\rm H}_{2,S}} - C_{{\rm eq,}a}} \right) $$\end{document}This type of kinetic equation indicates that during hydride formation in a slurry a surface process is the rate-determining step, which was confirmed by the observed influence of the solvent. Desorption of hydrogen can be described best with a shrinking core relation:\documentclass{article}\pagestyle{empty}\begin{document}$$ 1 - \left({1 - X} \right)^{1/3} = k_d ln\left({\frac{{P_{eq,d}}}{{P_{H_2}}}} \right)t $$\end{document}The phase transformation at the β/α boundary appears to be the rate-determining step. Alloys with higher aluminum contents produce a lower reaction rate constant.
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    AIChE Journal 39 (1993), S. 359-360 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 361-365 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993) 
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    AIChE Journal 39 (1993), S. 387-396 
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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: We calculate permeabilities for a class of granular porous media derived from a real, disordered packing of equal spheres. The entire structure, including pore space, of these media is completely specified by the radii and spatial locations of the constituent grains. When geometric nearest neighbor grains are grouped together, the structure may be subdivided into pore bodies and pore throats in a natural and unambiguous way. From this subdivision we can establish a network of flow paths whose geometry and topology are completely specified, so that permeability and other transport coefficients can be calculated directly and without any adjustable parameters. The calculations focus on processes that form porous media, rather than on specific examples of such media. Hence, the approach is essentially predictive, rather than correlative. No additional measurements (such as capillary pressure data or pore system data from thin sections) are required, and correlations between permeability and other properties are not used. Predicted permeabilities match measurements on sandstone samples similar to the model perous media studied here over a wide range of porosity. Geometrical attributes of the network representation of the pore space of the model media are found to be spatially correlated. This departure from randomness significantly affects permeability. The agreement between predictions and measurements suggests that spatial correlation is inherent in granular porous media and that uncorrelated network models are therefore unlikely to be physically representative of such media.
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    AIChE Journal 39 (1993), S. 369-386 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nonlinear transport processes in disordered systems such as porous media and heterogeneous solids are studied, which are represented by two- or three-dimensional networks of interconnected bonds, by a Bethe network (a branching network with no closed loops) of a given coordination number, or by a continuum in which circular or spherical inclusions have been inserted at random. The bonds represent the pores of the pore space, or the conducting and insulating regions of a disordered solid, to which we assign effective properties (radii or conductances) selected at random from a probability density function. Three types of nonlinear transport processes are considered. (1) The relation between the current q and the potential gradient v is of power-law type (as in, for example, flow of power-law fluids or the electric current in doped polycrystalline semiconductors). (2) The relation between q and v is piecewise linear, characterized by a threshold (as in flow of Bingham fluids or in mechanical or dielectric breakdown of composite solids). (3) A large v is imposed on the system, so that a linear transport theory is not valid. The behavioral study of the effective transport and topological properties of the system, such as the permeability, conductivity, diffusivity, and the shape of the samplespanning cluster of conducting paths shows that in all cases the concepts of percolation theory play a prominent role, even if the system is well connected and percolation may seem not to play any role. For most cases, new effective-medium approximations (EMAs) are derived for estimating effective transport properties. Compared to the case of linear transport, new EMAs are considerably more accurate in predicting the scaling properties of the transport coefficients near a critical point such as the percolation threshold. For a power-law transport process, an exact solution is also derived for the Bethe networks. Using the concepts of percolation theory, scaling laws relating the effective properties to various regimes of transport and to topological properties of the system are also given. A relation between the volumetric flow rate of a power-law fluid in porous media and the macroscopic pressure drop is derived, which contains no adjustable parameter and is valid at any porosity. To test the accuracy of our analytical predictions, Monte Carlo simulations are carried out for several cases. In most cases, good agreement is found between the simulation results and predictions. The extension of the results to other types of nonlinearities is also discussed.
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    AIChE Journal 39 (1993), S. 663-676 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Monte Carlo simulation results for binary mixtures of diatomic molecules with spheres, diatomic molecules of different bond lengths, and triatomic molecules with spheres, all interacting with the site-site Lennard-Jones potential, were obtained at three different volume ratios and a range of densities and compositions. We report the configurational internal energy of the mixture and of the 1-1, 1-2 and 2-2 pairs, and the compressibility factors at 195 state points. The site-site correlation functions also computed are available from the authors. Equations of state derived previously (Sowers and Sandler, 1991, 1992) for pure site-site Lennard-Jones fluids from a combination of perturbation theory and a three-parameter corresponding states principle are extended to mixtures using simple one-fluid mixing rules. These simple mixing rules allow us to make satisfactory predictions of the compressibilities computed from simulation without the use of binary interaction parameters. We also show that the effect of composition on the perturbation free energy βAp/N not accounted for by one-fluid mixing rules is quite small, and therefore a more complicated mixing rule is not necessary in our equations of state for the mixtures studied.
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  • 88
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    AIChE Journal 39 (1993), S. 689-694 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 677-688 
    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 isothermal vapor liquid equilibrium data were measured for the propane-1-propanol system at 81.6, 105.2, and 120.1° C in a static equilibrium cell with liquid-phase sampling by a piston-driven sampling rod and homogenizing the sample with a static jet mixer. The vapor phase was sampled by releasing it into an evacuated manifold, and the gas chromatograph was calibrated with a new variable volumetric device. Satisfactory modeling was achieved with the combined method (Wichterle, 1978b) using the UNIQUAC equation with equations of state: the group contribution EOS (Skjold-Jorgenson, 1986), Peng-Robinson EOS (Peng Robinson, 1976) or the two-parameter Virial EOS. Differences between the measured and calculated vapor-phase mole fractions, however, were signficant for the lower pressure regions of the 81.6 and 120.1° C isotherms.UNIQUAC parameters aij, hitherto unavailable, with fairly strong temperature dependence in the 81.6 to 120.1° C range are proposed for the system. The covariance matrix indicated a significant correlation among the parameters. The classical mixing rule interaction parameters, σij, required for the original Peng-Robinson EOS in the combined method were obtained using the direct method (Wichterle, 1978a) and were temperature-independent for the isotherms for which the propane was supercritical. The possibility of propane/1-propanol immiscibility was theoretically examined according to the criteria of Baker et al. (1982). The plots of Gibbs energy of mixing vs. phase mole fractions did not indicate liquid-phase splitting, but the inferences are EOS-dependent and must await visual confirmation. Our earlier vaporphase thermodynamic consistency test (1991a) indicated the data for all three data sets not to be inconsistent.
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    AIChE Journal 39 (1993), S. 707-710 
    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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  • 91
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    AIChE Journal 39 (1993), S. 711-714 
    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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  • 92
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    AIChE Journal 39 (1993), S. 715-719 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 93
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    AIChE Journal 39 (1993), S. 913-917 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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    AIChE Journal 39 (1993), S. 714-714 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 727-727 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 39 (1993), S. 727-728 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 924-924 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 728-729 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 39 (1993), S. 730-731 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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