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  • 101
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 3442-3457 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Of importance to geothermal energy development, oil, gas and mineral recovery, and waste storage is the characterization of the dissolution rate of host reservoir rock as a function of temperature, pressure and liquid-phase composition. As a major constitutive mineral in natural geologic systems, quartz was selected for study. Dissolution experiments were carried out in a continuous-flow, titanium autoclave reactor system at 100-200°C in various chemical environments. Acidification to pH 1.1 using nitric acid showed very little effect on the quartz dissolution rate. The effect of hydroxide ion concentration and ionic strength were evaluated in NaOH, NaOH/NaCl and NaOH/Na2SO4 solutions. The fractional-order dependency of the quartz dissolution rate on hydroxide ion and sodium ion (or ionic strength) concentration was determined in NaOH/NaCl solutions. The results that extend the available range of kinetic data for quartz generally agree with previous work. The observed fractional-order kinetics were qualitatively described using classical adsorption isotherms. No significant variation in the apparent reaction order of the hydroxide ion with increasing temperature could be determined due to the scatter in the data. Quartz dissolution rates were slower by about 40% in NaOH/Na2SO4 solutions than in NaOH/NaCl solutions at sodium concentrations higher than 0.01 molal. The apparent activation energy from 100 to 200°C in NaOH/NaCl solutions up to 0.01 molal hydroxide ion and 0.1 molal sodium ion was estimated to be 72 (±6) kJ/mol.
    Additional Material: 15 Ill.
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  • 102
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 3477-3483 
    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 intrinsic nitridation kinetics of high-purity silicon solid to form silicon nitride were determined by thermogravimetric analysis technique. The initial rate method was used to avoid kinetics falsification due to intraparticle diffusion limitation caused by the formation of silicon nitride layer around the silicon particles. Relatively small sample sizes were used to eliminate the interparticle diffusion limitation (compact effect) that becomes important as the reaction proceeds, owing to the expansion of the individual particles and filling of the initial pores within the compact. The effect of hydrogen addition to the nitriding gas, as well as the influence of the flow rate, on the reaction progress was also investigated.
    Additional Material: 11 Ill.
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  • 103
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A thermodynamics-based equilibrium model was developed to describe ion exchange equilibria of strong and weak electrolytes. It is applicable to binary and multicomponent systems, using selectivity coefficients for all ion pairs and distribution coefficients for all neutral species as parameters. The model was successfully tested for a strong-base anion exchange resin with the strong electrolyte NaCl and the weak electrolytes acetic acid and N-acetylmethionine in a wide concentration range. Compared to conventional models, this model is more advantageous because it takes into account the uptake of all species, counterions as well coions and neutral species, thus making it possible to calculate the intraparticle pH. Especially when weak electrolytes are involved and when electrolyte concentrations strongly exceed the resin capacity, it is superior to conventional ones, whereas for dilute systems it converges to the conventional stoichiometric displacement model.
    Additional Material: 9 Ill.
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  • 104
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 1901-1910 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new process for extractive separation with supercritical fluids is described. It is characterized by mixing a liquid feed with a dense gas in a special mixing device and the formation of spray particles when this mixture is injected into an extraction zone where the fluid phase is loaded with the extracts. By dividing the extraction into two process steps, mixing and loading, it is possible to adjust the devices and apparatuses for different media. For example, a static mixer or a fluid-assist atomizer can be used as mixing devices. Since the viscosity behavior of the mixture and the surface tension in dense gases are important for the formation of spray particles, carbon dioxide was measured at pressures up to 70 MPa and the geometry of the extraction zone was optimized by residence times and fluid dynamics.Two different materials were tested in an apparatus on a semiindustrial scale with different mixing devices and extraction zones. By measuring fluid loading in the extraction zone, the mass-transfer parameter of a mathematical extraction model could be adapted. The model considers particle formation in the mixing zone, the fluid dynamic in the loading zone, and the mass transfer between spray particles and fluid phase. Calculated concentration profiles make it possible to determine the residence time and the size of the extraction zone for given geometries and fluid dynamics.
    Additional Material: 14 Ill.
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  • 105
    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 column dynamics of simple ion-exchange processes involving acetic acid and N-acetylmethionine were studied using a strong-base anion exchange resin to reveal the complex relation between pH, concentration, equilibrium isotherms, and chromatographic separation in ion-exchange chromatography of weak electrolytes. Changing either the influent pH or the concentration, while keeping the other variable constant, led to considerable effluent concentration and pH fluctuations, respectively. This behavior is caused mainly by the uptake of undissociated acids. To describe these phenomena quantitatively, a rigorous thermodynamics-based equilibrium model for ion exchange, including Donnan potential and reaction equilibria, was incorporated into a fixed-bed model. Experimental results can be described well by this dynamic model, which is superior to conventional models due to its explicit incorporation of coions and partitioning of neutral species. It has great potential for optimizing chromatographic separations of weak electrolyte solutions.
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  • 106
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 1889-1900 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Gas-liquid-solid inverse fluidized beds were studied, in which the gas and the continuous liquid phase flow countercurrently fluidizing particles that are lighter than the liquid. Conductivity and static pressure measurements were combined to provide the vertical profiles of the gas, liquid and solid holdup, in beds of 4- or 6-mm polypropylene particles with a density of about 870 kg/m3. Various bed heights were obtained with different measurement methods. The minimum fluidization velocity was estimated using the bed static pressure gradient. A new transition velocity, called the uniform fluidization velocity, was identified using conductivity measurements. This is the superficial liquid velocity at which the fluidization quality becomes the same throughout the bed.
    Additional Material: 25 Ill.
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  • 107
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 1968-1976 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: NO reduction through heterogeneous mechanisms is a major concern when coal or lignite is used as reburning fuel. Reburning was simulated in an alumina flow reactor operated with a synthetic flue gas at a stoichiometric ratio of 1.1, at 1,100°C and with a residence time of approximately 0.2 s. Reburning fuels used include methane, one bituminous coal, two lignites, chars derived from the bituminous coal and two lignites, and the bituminous coal char impregnated with CaO. Reburning with chars indicates that heterogeneous mechanisms are more important than homogeneous mechanisms when lignites are used. This high reactivity renders lignite char an even more effective reburning fuel than the parent lignite, while char from the bituminous coal produces little activities at stoichiometric ratios above 0.75. Bituminous coal char impregnated with CaO demonstrates higher NO reduction efficiency than the original char. Effects of SR on NO reductions imply that oxygen atoms, required for the NO and HCN conversions in homogeneous mechanisms, are not required in heterogeneous mechanisms. In fact, they inhibit the surface NO reduction. The first-level kinetic analysis indicates that the surface area is not the only contributor to a remarkable increase in NO reduction of lignite char, and chars of different origins seem to follow different mechanisms or to have different controlling steps in the overall reaction scheme.
    Additional Material: 8 Ill.
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  • 108
    Electronic Resource
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 2014-2024 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Geometrical properties of the pore-solid interfaces of devolatilized charcoals from the pyrolysis of fuel woods in a bench-scale fluidized-bed reactor were investigated through small-angle X-ray scattering. Specifically, surface morphological features of the interfaces were characterized by a single parameter indicative of the degree of surface roughness, that is, the surface fractal dimension, dSF, at various retention times. The surface fractal dimensions of the original wood samples prior to devolatilization were approximately identical for all species within the range between 2.00 and 2.15, over a length scale from 55 to 600 Å, and those for the respective charcoals from these wood samples were influenced to different degrees by the retention time, τ, in the reactor. The dSF's of the mesopores of charcoals of all the species attained maxima at a value of τ equal to 35 s and decreased subsequently with an increase in τ. The analysis of this unexpected trend was facilitated by the values of the mean radii of gyration of the pores, estimated through the Guinier plots. The results imply that when the retention time of the charcoals in the reactor is prolonged, the mechanism of pore enlargement and smoothening of the interfaces can play a dominant role in altering the surface morphology and thereby influence significantly the kinetics of chemical reactions in heterogeneous porous systems.
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  • 109
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 2303-2307 
    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 attempt was made to simulate carbon gasification with the aid of molecular orbital theory. A simple Hückel method was applied to calculate molecular orbitals of a large polynuclear aromatic molecule, which was employed as a model crystallite for carbon. A free valence at each carbon atom in model crystallites of varying size and shape was determined, and this value was taken as a measure of reaction probability for the Monte Carlo simulation. Simulation of carbon gasification was performed by removing the carbon atoms from the model crystallites according to their corresponding reaction probabilities. This simulation made it possible to visualize how the shape of carbon crystallite is changed during gasification. It was found that the specific gasification rate depends on molecular size, but is essentially independent of the geometry of the starting model crystallite.
    Additional Material: 7 Ill.
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  • 110
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 2327-2334 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A comparison is made of the capabilities of various equation of state (EOS) + excess free energy (Gex) models in representing the activity-coefficient models they incorporate. Such EOS models need to reproduce the excess Gibbs free energy behavior of the activity-coefficient models as closely as possible in order to represent low-pressure vapor-liquid equilibrium behavior of complex mixtures accurately, and also to make accurate the vapor-liquid predictions at higher temperatures and pressures using only low-pressure information. It is demonstrated that the EOS models that use the excess Helmholtz free energy instead of the excess Gibbs free energy, and that combine the EOS with activity-coefficient models at the infinite pressure limit, are successful for calculations of the type just described.
    Additional Material: 10 Ill.
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  • 111
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 2335-2353 
    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 molecular-thermodynamic analysis is directed toward predicting the partitioning of aqueous proteins into charged hydrogels. This analysis takes into account size exclusion by the network, electrostatic interactions, and the osmotic-pressure difference between a hydrogel and its surrounding solution. Electrostatic interactions in the polyelectrolyte gel can be described by Debye - Hückel theory, or the Mean Spherical Approximation, or Katchalsky's cell model for polyelectrolyte solutions. The cell model gives best agreement with experimental partition coefficients for cytochrome c. The quasi-electrostatic potential difference between a gel and its surrounding solution demonstrates how the electrostatic contribution to the protein partition coefficient depends on protein charge, gel-charge density, and solution ionic strength. Finally, a qualitative guide is presented for design of a polyelectrolyte gel such that it exhibits specified swelling and partitioning properties.
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  • 112
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 2369-2373 
    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: 6 Ill.
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  • 113
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 2382-2387 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 114
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 115
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 1-1 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 116
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 2-9 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Diffusion of carbon dioxide through silicone-polycarbonate membranes containing oriented mica flakes is proportional to the square of the volume fraction of the flakes, to the square of the aspect ratio, and to the square of the cosine of the angle at which the flakes are oriented. These experiments are consistent with Monte Carlo simulations. The simulations allow investigation of more complex geometries, including other flake orientations and polydisperse flake sizes.
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  • 117
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 10-22 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Formation of asphalt aggregates and their deposition on the pore surfaces of a porous medium, which alter the structure of the medium and its effective properties, is a critical problem to catalytic and oil recovery and refinery processes. Extensive new experimental data for the amount of precipitated asphalt formed with crude oil and various solvents are presented. Results indicate that, contrary to the previous assumptions, asphalt formation is at best partially reversible. A thermodynamic model based on the Flory-Huggins theory of polymer solutions is used, together with the Soave equation of state, to predict the data. Critical evaluation of the model shows that its predictions do not agree well with our data. As an alternative, we propose a new model that employs a scaling equation, somewhat similar to those encountered in aggregation and gelation phenomena. The scaling function takes on a very simple form, and its predictions are in very good agreement with the data. It also predicts that the onset of precipitation may obey a simple universal equation.
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  • 118
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 23-41 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An integral-spectral formulation for laminar reacting flows in tubular geometry (tubular Poiseuille flows) is introduced and performed within an operator-theoretic frame-work where the original convective-diffusive differential transport problem coupled with reaction is inverted to give an integral equation. This equation is of second kind and of the Volterra type with respect to the axial coordinate of the tube with a kernel given by Green's function. Green's function is identified by a methodology that gives the Mercier spectral expansion in terms of eigenvalues and eigenfunctions of the Stürm-Liouville problem in the radial variable of the tube. Eigenvalue problems for both Dirichlet and von Neumann boundary conditions are solved in terms of analytical functions (Poiseuille functions) and compared with the values found in the literature. The groundwork is set for future applications of the methodology to solving a wide variety of problems in convective-diffusive transport and reaction. Examples with wall and bulk chemical reaction are given to illustrate the technique.
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  • 119
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 42-54 
    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 laser-Doppler velocimetry (LDV) apparatus and a computational fluid dynamic (CFD) software package (FLUENT) were used to experimentally determine and numerically predict the velocities in a baffled vessel agitated by one or two 45° pitched-blade turbines. The flow characteristics in the impeller regions were measured by LDV and used as boundary conditions in the numerical computations. Turbulence effects were simulated using either the k-ε model or algebraic stress model (ASM). The CFD predictions were compared to the LDV measurements in terms of average velocities in all three directions as well as turbulent kinetic energies. Predictions based on ASM were typically in closer agreement with the experimental data than those based on the k-ε model. Flow patterns in both configurations were dominated by the axial and tangential components. The presence of the upper impeller altered the flow considerably, producing a strong vertical recirculation pattern between the impellers and significantly reducing the circulation flow below the lower impeller.
    Additional Material: 14 Ill.
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  • 120
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 671-682 
    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 absorption of Cl2 into aqueous bicarbonate and aqueous hydroxide solutions was studied both experimentally and theoretically. The rate coefficient of the reaction between Cl2 and OH- was estimated over the temperature range of 293-312 K and fitted by the Arrhenius equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{24} = 3.56*10^{11} \exp \left({\frac{{ - 1,617}}{T}} \right) $$\end{document}.If Cl2 were assumed to react only with water and OH- in an aqueous bicarbonate solution, the predicted absorption rate would be much lower than that experimentally measured. This suggests that Cl2 reacts with HCO3- in an aqueous bicarbonate solution. The rate coefficient of the reaction between Cl2 and HCO3- was estimated over the temperature range of 293-313 K and fitted by the Arrhenius equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{21} = 5.63*10^{10} \exp \left({\frac{{ - 4,925}}{T}} \right) $$\end{document}.More importantly, under absorption conditions, the amount of hydroxide consumed for absorbing a specific amount of Cl2 into an aqueous hydroxide solution is almost twice the amount of bicarbonate consumed for absorbing the same amount of Cl2 into an aqueous bicarbonate solution.
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  • 121
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 147-153 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: L-Isoleucine and the isomorphic amino acids L-leucine and L-valine serve as a model system in the examination of the effects of impurities on the purity and morphology of crystals recovered from batch crystallizations. Factors are determined that influence crystal purity and, concomitantly, crystal size and shape. Characteristics of the L-isoleucine crystal are determined by X-ray analysis and compare favorably with the literature. These and literature characteristics of L-leucine and L-valine are used in simulations to evaluate possible mechanisms by which lattice substitutions with impurities lead to size and morphological changes.
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  • 122
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 131-146 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Recuperative parametric pumping in adsorptive membranes, a cyclical adsorptive separation process, can lead to two distinct mechanisms of separation: rejection and preferential transport. During rejection, the adsorptive membrane rejects an adsorbing solute while permitting the transport of nonadsorbing solutes. During preferential transport the reverse occurs; the adsorptive membrane selectively transports an adsorbing solute while preventing the transport of nonadsorbing solutes. Switching from rejection to preferential transport can be accomplished by merely decreasing the ratio of the stroke volume (cyclical volume of solution pumped into and out of the membrane) to the membrane void volume. Preferential transport, earlier called an “inverse separation,” results from the adsorbing solute crossing over from an adsorbing to a desorbing region in the interior of the membrane and is governed by the shape of the equilibrium isotherms and by process variables. In experiments with lysozyme and a membrane chromatography cartridge, selectivities obtained by preferential transport were on the order of 5 and agreed with theoretical predictions. Theoretical predictions suggest that to further improve separation by preferential transport, experiments need to be conducted on low dispersion membranes (Pe 〉 104) and that both rejection and preferential transport can lead to continuous concentrated streams of the adsorbing solutes.
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  • 123
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 161-175 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new approach to cation-exchange kinetics views ion-exchange resin as an aggregate of uniform cylindrical pores. Ion exchange occurs at the pore surface. The counterions dissociate only partially from the fixed sites, and the charge created on the pore surface is balanced by the counterions in the electrical double layer. Thus, any cross section of a pore consists of an annular double-layer region and a central core region. Electroneutrality prevails in the core region through an influx of coions. Diffusion of ions through both regions is considered. The complete model incorporating these ideas for kinetics of monovalent cation exchange was tested with our experimental data as well as with the reported data. The pore diffusion coefficients used in the model are free ionic diffusion coefficients corrected for the tortuosity factor of the pores. Unknown parameters of the model are the degree of dissociation of counterions from the fixed sites of the pore (fσ), and the film thickness (δ). Both parameters are insensitive to the type of counterions, solution concentration, and the direction of exchange. Further, fσ appears to be a characteristic property of resin alone. Superiority of the developed model over the previous models is established.
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  • 124
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 187-203 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Discrete-time nonlinear feedback control laws are derived for multivariable nonlinear processes, whose “delay-free” parts are minimum phase. These include mixed error-and state-feedback, error-feedback, and mixed error- and output-feedback laws, which can induce linear input-output closed-loop response. This study is carried out within the framework of the discrete-time globally linearizing control. The broader class of nonlinear processes, in which controlled outputs as well as some other process variables are measured, are also considered. A mixed error- and output-feedback control law is derived for this class of processes. The conditions under which the mixed error- and output-feedback can be applied to a process operating at or around an open-loop unstable equilibrium point are determined. The application and performance of the derived control laws are illustrated by the numerical simulation of a chemical reactor.
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  • 125
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 753-766 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new methodology for gage control of sheet and film processes is presented. A linear process model is developed that is capable of describing many of the interesting features of the process, including a noisy and moving gage sensor, significant process noise, strong coupling between the gage in different lanes, constraints on the actuators, and significant time delay between the actuators and the sensor. An automatic control of this process given this model form is designed. Novel features of the controller are that it can contend with information from a moving sensor and handle hard constraints on the actuators. Control performance and robustness to noise are demonstrated favorably via simulations.
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  • 126
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 742-752 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: With the growing environmental concern, it is necessary to improve process simulation and develop design tools to account for environmental factors in the synthesis of large-scale chemical processes. A major obstacle in tackling this problem is uncertainties in some of the technical and economic parameters, which lead to uncertainties in design, plant performance, and cost estimates. Further, a conceptual process design involves the identification of an optimal flowsheet structure from many alternatives stituting the “superstructure.” Synthesis and optimization of large-scale processes involving uncertainties often require considerable computational effort. A novel algorithm presented here is based on simulated annealing for the process synthesis of large-scale flowsheets having several configurations and considers uncertainties in the process design systematically. This new “stochastic annealing algorithm,” provides an efficient approach to stochastic synthesis problems by incorporating a penalty term in the objective function and balances the trade-off between accuracy and efficiency based on the annealing temperature. It has been used to study a benchmark synthesis problem in the HDA process. Savings of up to 80% in CPU time has been achieved without significant loss of solution precision with stochastic annealing, compared to simulated annealing with a fixed sample size. It can be applied to analyze efficiently any complex process flowsheet and provide valuable insights into process feasibility based on optimal design, plant performance, and uncertainty issues.
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  • 127
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 332-346 
    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 flows generated in vessels stirred by two Rushton impellers were investigated in two vessels of diameter (T) 100 and 294 mm with impellers of diameter D = T/3 using flow visualization, power consumption, mixing time, and 360° ensemble-averaged and 1° angle-resolved LDA measurement techniques. The flows depended strongly on the clearance of the lower impeller above the base of the vessel (C1), the separation between the impellers (C2), and the submergence (C3) of the upper impeller below the top of the liquid column height (H). When these distances were varied, three stable and four unstable flow patterns were observed. Comparisons between the two LDA techniques showed that while the 360° ensemble-averaged measurements are useful for characterizing the overall flow structure and turbulence levels in the vessel, care must be exercised when interpreting such data, since in the impeller region they include periodic variations in the mean velocity in addition to the turbulent fluctuations. The trailing vortex structure and flow periodicity produced by the Rushton impellers is shown to decay significantly within a cylindrical region of height 1.2D and radius 1.0D centered around the middle of the vessel, when C1 = C2 = T/3. The turbulence structure within this region is anisotropic, while outside this region it might be considered mostly isotropic. The main flow features scaled well between the vessels.
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  • 128
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    AIChE Journal 42 (1996), S. 1077-1087 
    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 ignition-extinction behavior in the oxidation of methane, ethane, propane and isobutane, as well as of ethylene and propylene over a platinum-foil catalyst was studied over the entire range of fuel/air ratios at atmospheric pressure. Ignition and extinction of the heterogeneous surface reaction, homogeneous ignition and the autothermal behavior of these fuel-air mixtures were investigated. The results show a common trend in the ignition extinction behavior of the alkanes and a different trend for the olefins. This is discussed in terms of a simple model, which correctly predicts the composition dependence of the surface ignition curve for reasonable values of parameters, indicating a mainly oxygen-covered surface during ignition of the alkanes and a mainly hydrocarbon-covered surface in the case of the olefins. Different branches of the complete bifurcation diagrams are discussed separately, allowing qualitative conclusions about the catalytic activity of Pt for the oxidation reactions of different fuels.
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  • 129
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    AIChE Journal 42 (1996), S. 1041-1068 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The study of spatial structures in heterogeneous reactors is a challenging academic topic, revealing patterns that differ from those known to exist in reaction-diffusion systems exposed to uniform conditions, as well as a practical problem that should affect design and operation procedures of commercial reactors like the catalytic convertor. Experimental observations and mathematical models of spatiotemporal patterns in high-pressure catalytic reactors are reviewed. Patterns in high-pressure reactors, in which thermal effects provide the positive feedback, as well as the long-range communication, usually emerge due to global interaction. Patterns are classified comprehensively by considering reactors of increasing degree of complexity: a wire or ribbon exposed to uniform conditions, a globally coupled catalyst in a mixed reactor or in a control loop, and a fixed bed in which interaction by convection occurs only in one direction. Catalytic wires are not expected to exhibit sustained patterns in the absence of global interaction. Global interactions by external control or gas-phase coupling are shown experimentally and analytically to induce a rich plethora of patterns. Complex motions were simulated to occur due to the interaction of convection, conduction and reaction in a fixed-bed; only a few of these patterns were experimentally observed. Directions for future research are suggested.
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  • 130
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    AIChE Journal 42 (1996), S. 1088-1094 
    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 ignited state is associated with a thin reaction zone and a steep temperature gradient ahead of the front. The stability of this front is analyzed for small radial and azimuthal perturbations. The near-equidiffusional assumption is made, and the deviation of the Lewis number from unity is considered as the bifurcation parameter. The analysis shows that the planar front becomes unstable at Lewis numbers above unity after a Hopf bifurcation. The oscillatory front collapses into hot spots or rings which oscillate around the axial axis. For Lewis numbers less than one, a steady-state cellular front structure is found.
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  • 131
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    AIChE Journal 42 (1996), S. 1095-1100 
    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 novel reactor for the modification of a porous hollow-fiber membrane up to 1 m in length is presented. The polyethylene hollow fiber irradiated with an electron beam was exposed to the vapor of an epoxy-group-containing vinyl monomer (glycidyl methacrylate) in a cylindrical reactor rotated at 1 rpm. Construction of the hollow fibers resulted in a diffusion-controlled reaction system, which led to the nonuniformity of degree of grafting (dg), whereas the shuffling of the hollow fibers by rotating the cylindrical reactor provided a higher reactivity (dg = 110% for 100 min at 300 K) and uniformity (standard deviation = 4.5%) of dg.
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  • 132
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    AIChE Journal 42 (1996), S. 1116-1126 
    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 Helmholtz energy F is written as the sum F = FH + FA + FPol, where FH is the hard-body contribution, FA the attractive dispersion force contribution, and FPol either the quadrupolar or dipolar contribution. Here, a new expression for FA is constructed by a simultaneous correlation of experimental data of methane, oxygen, and ethane. The resulting equations for F with only three or four substance-specific parameters are tested for several nonpolar, quadrupolar, and dipolar fluids. In the correlation of large data sets good results are obtained. The significance of the approach, however, is in the good to excellent prediction of all thermodynamic properties in the whole fluid region based on a parameter fit to only four experimental data - two vapor pressures and two saturated liquid densities.
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  • 133
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    AIChE Journal 42 (1996), S. 1108-1115 
    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 lab-scale nonflowing reactor was built to study chemical vapor deposition reactions. Mass spectrometry is used to follow reaction pathways and to determine instantaneous reaction rates throughout film growth. In each experiment, the kinetic rate dependence on concentration for a wide range of concentrations is observed as reactants convert to products. This method of obtaining kinetic data is efficient in terms of sample loading, gas usage, and time, since over 200 instantaneous rate/composition pairs can be determined from one 30-min deposition. Because the rate is determined from gas-mass balance, rather than film-thickness measurements, an unlimited number of rate studies can be made on one sample. As a test case, the SiH4 reduction of WF6, used to deposit tungsten during integrated-circuit production, was investigated in the 0.64-L nonflowing laboratory reactor. Gas compositions were measured 2 mm from the growing surface, throughout time, with a mass spectrometer equipped with a capillary sampling tube. Tungsten was deposited on the 95°C surface, and SiHF3 was the primary silicon fluoride reaction product for most tested conditions. A multiple-regression analysis of 1,975 instantaneous composition/rate pairs gives orders of 1.22 in silane, 0.27 in hydrogen, and -2.17 in WF6. The ratio of SiF4 to SiHF3 stays low and constant until the gas becomes silane-rich. The evolution of the instantaneous rate over time implies that a minimal level of thermal activation of the reactive gases is necessary for the deposition to be surface-rate-limited. Preliminary heat-transfer models of the wire substrate imply that heat transfer to the gas phase is in the Knudsen regime.
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  • 134
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    AIChE Journal 42 (1996), S. 1139-1148 
    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 behavior of a reverse-flow reactor was studied for the purification of polluted air by catalytic combustion. A heterogeneous one-dimensional model was extended with a heat balance for the reactor wall. An overall heat transport term is included to account for the small heat losses in radial direction.The calculations are compared to experimental data without using fit parameters. The agreement between simulations and experiments is generally good. Discrepancies can be explained mainly by inaccurate kinetic data and experimental uncertainties. At low gas velocities and for small reactor diameters, the one-dimensional model failed and a two-dimensional model must be developed to improve the predictive potential.
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  • 135
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    AIChE Journal 42 (1996), S. 1149-1152 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: No Abstarct.
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  • 136
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    AIChE Journal 42 (1996), S. 1127-1138 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dynamic projections from the surface of many motile cell types provide for variable contact with the extracellular environment and can be important in regulating cell migration events. For example, during nerve development and regeneration, the sensory motile tip of the axon exhibits long, slender filopodia projecting from the growth cone periphery. Extension and retraction of these filopodia continually remodel the points of contact between axon and surroundings. Experimental studies show that filopodial contact with specific extracellular features can guide subsequent growth cone migration, suggesting a potentially important means of engineering nerve growth to repair nerve injury or construct biological neural networks. A simulation model is presented of the dynamic filopodial structure on the nerve growth cone based on recent experimental characterization. The model is analyzed to obtain quantitative relationships between average filopodial characteristics, which are commonly measured experimental quantities, and the underlying parameters of individual filopodium dynamics. It is then applied to simulate encounter between a growth cone and its target due to filopodial dynamics alone. Filopodial contribution to growth cone-target encounter is summarized in terms of a mean encounter time that is reminiscent of a first passage time for a diffusing particle. The parametric relationships in this study provide a basis for further investigation of filopodial-mediated mechanisms in nerve growth and other cellular processes.
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    AIChE Journal 42 (1996), S. 1153-1156 
    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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  • 138
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    AIChE Journal 42 (1996), S. 1157-1163 
    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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  • 139
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    AIChE Journal 42 (1996), S. 1170-1173 
    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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  • 140
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    AIChE Journal 42 (1996), S. 1164-1169 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 7 Ill.
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  • 141
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    AIChE Journal 42 (1996), S. 154-160 
    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 is intended as a complement to a recent article in this journal, “Comparative Study of Flow Schemes for a Simulated Countercurrent Adsorption Separation Process” by Ching et al. (1992). These authors carried out experiments on continuous separation of three carbohydrate mixtures with both the usual four-section scheme and a three-section scheme: fructose dextran (MW ≌ 9,400), raffinose dextran (MW = 6,000), and fructose-raffinose. These two schemes were modeled as equivalent true countercurrent systems. From the experiments and model results they conclude that the equivalent true countercurrent model is fully adapted to represent the four-section scheme, but a major discrepancy arises with the three-section scheme: the raffinate concentration is not correctly predicted.From these results it may be concluded that when a physically meaningful modeling of the equivalent true countercurrent is realized, the apparent discrepancy disappears. From another standpoint, such a mismatch between the experiments and model predictions would not have been observed with a model that considers the periodic port motion. Such a model foresees a cyclic steady state where extract and raffinate compositions vary throughout the period T; they can be considered as constant only when averaged over the period. It is worth comparing the results of these two models, especially when the equivalent countercurrent representation is not very close to the physical phenomenon it should represent.We agree with their major finding that a three-zone scheme represents necessarily a higher desorbent demand than a four-zone scheme.
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  • 142
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    AIChE Journal 42 (1996), S. 176-186 
    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 stable adaptive control strategy is suggested for a class of continuous-flow bioreactor processes described by Monod kinetics with two unknown parameters, one of which appears nonlinearly. Similarly, as in the case of the previously reported adaptive controllers, the parametrization of the process model, in conjuction with the adaptive exponential feeding strategy and corresponding adaptive algorithms, results in a stable system in which the convergence of the output errors to zero is guaranteed. In the former, however, two major problems are encountered: (1) both output errors were used to adjust the controller parameters, which may yield unacceptable performance of the resulting adaptive system; (2) conditions under which the process output can assume only positive values are difficult to derive. Hence, a design of a stable adaptive controller is suggested, whose parameters are adjusted using only one of the output errors and that yields acceptable performance of the control system. With this method, conditions under which the process outputs can assume only positive values can be readily derived. These conditions in turn guarantee that the control input saturation at value zero cannot occur. In this context, two adaptive controllers are suggested, such that the resulting adaptive systems are stable and the control objective is met. The adaptive controller design relies on a convenient coordinate transformation, while the proof of stability is based on suitably chosen Lyapunov functions. The performance of the adaptive system is evaluated through computer simulations.
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  • 143
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    AIChE Journal 42 (1996), S. 232-238 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dissolution and crystal growth on the (010) cleavage surface of mineral gypsum have been studied by scanning force microscopy, which allows observation of surfaces while they are in contact with aqueous solutions. Etch pits formed on the (010) surface in contact with solutions undersaturated with respect to gypsum are oriented in relation to the [001] zone axis. Edges parallel to [001] are stable or move only slowly. Edges parallel to [100] and [101] move more rapidly. Crystal growth by migration of step edges is observed in contact with supersaturated solutions. The inhibition of crystal growth by phosphonate produces gross changes in the texture of steps and terraces.
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  • 144
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    AIChE Journal 42 (1996), S. 214-231 
    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 long-time behavior of a reaction mixture containing infinitely many species in isothermal continuous stirred tank reactors (CSTRs) is analyzed and contrasted with that in a plug-flow reactor (PFR). The reaction kinetics considered are irreversible first-order, irreversible coupled pseudo first-order, and reversible first-order. Asymptotic lumped kinetics for the mixture as a whole are developed as a function of feed properties and reactor type. Such lumped kinetics in many cases are of the power law form, with the exponent for a CSTR being lower than that for a PFR. Conditions under which non-power-law kinetics arise are given. Due to the wide spread of reactor residence times, the mixture in CSTRs admits a much richer variety of asymptotic possibilities than in the PFR. The results uncover some behavioral differences and relationships between CSTRs and a PFR for converting complex mixtures such as petroleum distillates or coal liquids.
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  • 145
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    AIChE Journal 42 (1996), S. 271-276 
    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: 8 Ill.
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  • 146
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    AIChE Journal 42 (1996), S. 277-284 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 147
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    AIChE Journal 42 (1996), S. 285-289 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 148
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    AIChE Journal 42 (1996), S. 296-297 
    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: 1 Ill.
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  • 149
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    AIChE Journal 42 (1996), S. 319-331 
    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 unified network model is formulated for predicting effective Fickian diffusivities of condensable vapors in porous media where capillary condensation and adsorption-desorption hysteresis occur. The model unifies the equilibrium theory based on the poreblocking interpretation of hysteresis in the interconnected network of pores and the percolation model of mass transport in the network with randomly interspersed regions for capillary condensation and surface flow. The Bethe network is used to represent the porous medium, and the effective medium theory is employed to obtain the effective diffusivity. Using the information on the connectivity and the positions of the closure points of the hysteresis loop enclosed by the equilibrium primary adsorption and primary desorption isotherms, the concentration dependence of the effective diffusivity is predicted. The model is applied to the systems water vapor-silica gel, water vapor-activated alumina, and literature data. It successfully predicts the concentration dependence of the effective diffusivity in the whole range of relative pressures for systems both with and without a peak in the diffusivity.
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  • 150
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    AIChE Journal 42 (1996), S. 347-358 
    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 and pressure fields and the effect of wall flux on these fields in a spiral channel are presented. As fluid flows inward through a spiral channel with constant gap and permeable walls, the streamwise flux decreases while the curvature increases. Thus, by balancing the stabilizing effect of wall suction with the destabilizing effect of increasing curvature, established vortices can be maintained along the spiral channel. This approach is used to prescribe spiral geometries with different wall fluxes. Using a weakly nonlinear stability analysis, the influence of wall flux on the characteristics of Dean vortices is obtained. The critical Dean number is reduced when suction is through the inner wall only, is slightly reduced when suction is equal through both walls, and is increased when suction is through the outer wall only. The magnitude of change is proportional to a ratio of small numbers that measures the importance of the effect of curvature. In membrane filtration applications the wall flux is typically 2 to 5 orders of magnitude less than the streamwise flow. If the radius of curvature of the channel is of the order of 100 times the channel gap, the effect on the critical Dean number is within 2% of the no-wall flux case. If the radius of curvature is sufficiently large, however, it is possible to observe effects on the critical Dean number that approach O(1) in magnitude for certain parameter ranges.
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    AIChE Journal 42 (1996), S. 359-368 
    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 of simultaneous heat and mass transfer presented describes drying with internal heat generation. Since a liquid expulsion phase is observed, a numerical procedure was developed to account for saturated and unsaturated zones and to model the liquid expulsion. The model was validated by a drainage experiment. An experimental rig was built to conduct microwave drying experiments in well-controlled conditions using capillary porous body (light concrete) as test material. Two types of drying (high and low power) were distinguished, depending on whether or not boiling occurred in the sample. The heat source term in the medium was determined from the experimental results. The numerical results agree with the experimental observations in terms of drying kinetics and transfer mechanisms. This allows a very accurate description of the transport phenomena and the liquid expulsion phase associated with high-power drying.
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    AIChE Journal 42 (1996), S. 369-382 
    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 computer-aided simulator of steady-state two-phase flow in consolidated porous media is developed. The porous medium is modeled as a 3-D pore network of suitably shaped and randomly sized unit cells of the constricted-tube type. The problem of two-phase flow is solved using the network approach. The wetting phase saturation, the viscosity ratio, the capillary number, and the probability of coalescence between two colliding ganglia are changed systematically, whereas the geometrical and topological characteristics of the porous medium and wettability (dynamic contact angles) are kept constant. In the range of the parameter values investigated, the flow behavior observed is ganglion population dynamics (intrinsically unsteady, but giving a time-averaged steady state). The mean ganglion size and fraction of the nonwetting phase in the form of stranded ganglia are studied as functions of the main dimensionless parameters. Fractional flows and relative permeabilities are determined and correlated with flow phenomena at pore level. Effects of the wetting phase saturation, the viscosity ratio, the capillary number, and the coalescence factor on relative permeabilities are examined.
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  • 153
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    AIChE Journal 42 (1996), S. 391-404 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model and numerical algorithm are developed to predict electrodeposition rates from a 2-D jet of electrolyte that impinges on a flat surface. The principal situations of interest are for applied voltages that produce current densities below the limiting current. The motion is assumed to be at high speed with the jet inducing a thin laminar boundary layer on the surface; a progressively thinner concentration layer and an electrochemical double layer near the surface are accounted for. Two cases, corresponding to a submerged and unsubmerged jet, are considered. A boundary integral method is used to compute the current density along the plate in a general iterative numerical procedure coupled to the solution of the hydrodynamic, concentration and electrochemical boundary layers. The results show that relatively high deposition rates occur near the point of impingement and that altering the jet angle relative to the surface influences local electrodeposition rates significantly.
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    AIChE Journal 42 (1996), S. 409-421 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A novel gas purification technique called rapid pressure swing absorption (RAPSAB) was developed by integrating the best features of membrane contacting, gas-liquid absorption, and pressure swing adsorption (PSA). In this cyclic separation process, a well-packed microporous hydrophobic hollow-fiber module was used to achieve nondispersive gas absorption from a high-pressure feed gas into a stationary absorbent liquid on the module shell side during a certain part of the cycle followed by desorption of absorbed gases from the liquid in the rest of the cycle. The total cycle time varies between 20 s and upwards. Separation of mixtures of N2 and CO2 (around 10%) where CO2 is the impurity to be removed was studied using absorbent liquids such as pure water and a 19.5% aqueous solution of diethanolamine (DEA). Three RAPSAB cycles studied differ in the absorption part. Virtually pure N2 streams were obtained with DEA as absorbent demonstrating the capability of bulk separation to very high levels of purification. Numerical models developed predict the extent of purification for pure water and the DEA solution for one of the simpler cycles. Model simulations describe the observed behavior well.
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    AIChE Journal 42 (1996), S. 431-439 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The crystallization of phenanthrene from toluene with carbon dioxide as the antisolvent gas is described. In the GAS process, a pressurized gas is dissolved into a liquid solvent, where it causes a volumetric expansion and lowers the solubility of the solute. Theoretical models are presented for the liquid-phase expansion and the solubility as a function of pressure and temperature. The Nývlt theory for batch crystallization is adapted to predict the pressure profile in the crystallizer needed to maintain a constant supersaturation and growth rate. Generation of seeds is accomplished via a pressure pulse at the saturation pressure. The average particle size of the phenanthrene could be varied from 160 to 540 μm. Creation of seeds doubles the particle size and reduces the coefficient of variation significantly. The residual amount of toluene in the crystals without treatment is approximately 70 ppm. The particles are agglomerates of phenanthrene crystals.
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  • 156
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    AIChE Journal 42 (1996), S. 440-454 
    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 high throughput and operating cost of the reactor provide the economic incentive in considering the on-line optimization of the LDPE tubular reactor. For an on-line optimization procedure it is crucial to develop a flexible and adaptive on-line parameter estimator, which based on the appropriate measurements from the reactor will adjust certain key model parameters so that the model can capture the actual reactor operation and reliably be used for the real-time optimization of the reactor performance. Various issues involved in developing the on-line estimator for such applications as the mathematical modeling of the reactor, the selection of the adjustable model parameters and reactor measurements, the decomposition of the problem according to the characteristic time constants of various disturbances, and the efficient and robust solution of the mathematical problem are discussed. The tools developed were successfully used on an EXXON high-pressure LDPE tubular reactor. Results from the numerical experiments that are compared with scaled data from a real reactor show that the estimated temperature profiles agree remarkably with those observed at various phases of the reactor operation.
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  • 157
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    AIChE Journal 42 (1996), S. 455-465 
    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 issues involving the methodology used for on-line control of product quality in batch manufacturing processes are addressed: the generation of fast, data-driven process models and the use of such process models for on-line feedback control of product quality. The methodology is investigated using the example of the control of dispersity and molecular weight distribution in a batch reactor for emulsion polymerization of vinyl acetate. An artifical neural network (ANN) is used as a model to predict the quality as a function of the manipulated variables and on-line measurements. This model is constructed using an augmented dataset that integrates experimental information and knowledge from a mathematical model. The proposed model is compared with other types such as a theoretical model whose key parameters are fitted to experimental data. The hybrid ANN is superior to the parameter-fitting approach for this case. Experimental and simulation studies confirm the advantage of using the proposed model and the predictive control algorithm.
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  • 158
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    AIChE Journal 42 (1996), S. 466-476 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Suppressing the influence of external disturbances on a process is the most common objective of a controller in a chemical plant. A control system that can keep the controlled variables at or near their set point and the manipulated variables lower than their prespecified maximum bounds in the face of load disturbances is wanted. A method is presented to design controllers with disturbance rejection specifications and limits over the control energy. This methodology is based on a special strategy to shape the structured singular value of a closed-loop transfer function matrix.
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  • 159
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    AIChE Journal 42 (1996), S. 477-492 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Effective utilization of measured process data requires efficient techniques for their compact storage and retrieval, as well as for extracting information on the process operation. Techniques for the on-line compression of process data were developed based on their contribution in time and in frequency using the theory of wavelets. Existing techniques for compression via wavelets and wavelet packets are inconvenient for on-line compression and are best suited for stationary signals. These methods were extended to the on-line decomposition and compression of nonstationary signals via time-varying wavelet packets. Various criteria for the selection of the best time-varying wavelet packet coefficients are derived. Explicit relationships among the compression ratio, local and global errors of approximation, and features in the signal were derived and used for efficient compression. Extensive case studies on industrial data demonstrate the superior performance of wavelet-based techniques as compared to existing piecewise linear techniques.
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  • 160
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    AIChE Journal 42 (1996), S. 493-502 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Neural-network-based control schemes are generally designed by replacing standard elements of the classic control schemes by feedforward neural networks. The introduction of discrete time recurrent networks, which are inherently dynamic systems, into those schemes can simplify the design of neural controllers. The concept of applying recurrent networks in indirect adaptive control schemes is described. A combined network cluster consisting of the control network and the model network is constructed to allow the use of the real-time recurrent learning algorithm. To demonstrate the feasibility of the method two simulation examples are presented.
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  • 161
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    AIChE Journal 42 (1996), S. 850-860 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Cartilage constructs were grown using isolated chondrocytes and biodegradable polymer scaffolds made of fibrous polyglycolic acid in the form of 1-cm-dia × 5-mm-thick discs. The scaffolds were seeded in a mixed cell suspension and cultured for up to 8 weeks under static or mixed tissue culture conditions in petri dishes and spinner flasks. Turbulent mixing significantly improved the biochemical compositions and altered morphologies of the cartilage constructs, which were the thickest ones cultured to date in vitro. Constructs from mixed cultures were more regular in shape and contained up to 70% more cells, 60% more sulfated glycosaminoglycan, and 125% more total collagen when compared to constructs from static cultures. Mixing also induced the formation of an outer capsule with multiple layers of elongated cells and collagen fibrils around the inner tissue phase, while statically grown constructs consisted of round cells embedded in cartilaginous matrix. Mixing during cell seeding and tissue culture is thus an important parameter for the cultivation of tissue-engineered cartilage in a range of sizes, shapes and compositions for a variety of clinical applications (e.g., fibrous cartilage for reconstructive surgery or articular cartilage for joint resurfacing).
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  • 162
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    AIChE Journal 42 (1996), S. 876-883 
    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 solid-state carbon monoxide sensor was fabricated using a 9% yttria-stabilized zirconia (YSZ) disc sandwiched between two platinum thin-film electrodes. One of the electrodes was coated with a thin layer of 7 CuO · 10 ZnO · 3 Al2O3 catalyst. The sensor showed limiting current behavior at an applied voltage between 0.5 and 1.2 V. Linear response was observed with carbon monoxide in a nitrogen-oxygen mixture at high temperature and limiting current conditions. The linear carbon monoxide concentration range increased with increase in the operating temperature and its sensitivity increased from 2.437 mA · atm-1 CO at 1,023 K to 10.771 at 1,093 K. These characteristics were adequately described by the proposed mathematical model relating the response to the rate processes occurring in the catalyst layer and in the electrochemical cell under limiting current conditions. The model showed that effective sensing and high sensitivity are best obtained using a catalyst with high catalytic activity toward the test solute and proper design and fabrication of the sensor to ensure its high diffusivity in the catalyst.
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    AIChE Journal 42 (1996), S. 889-891 
    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 42 (1996), S. 892-895 
    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 42 (1996), S. 884-888 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 166
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    AIChE Journal 42 (1996), S. 896-900 
    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: 6 Ill.
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  • 167
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    AIChE Journal 42 (1996) 
    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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  • 168
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    AIChE Journal 42 (1996), S. 910-920 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: New data on the variation of the diffusion coefficient with concentration in binary nonideal liquid mixtures are presented. The diffusion coefficients were measured with laser holography with an improved analysis procedure and are primarily in systems that form two liquid phases. The results show that for such systems the diffusion coefficient is constant if a chemical-potential driving force is used. If, however, the miscibility gap is wide, the Schreiner equation (Schreiner, 1922) is shown to be more accurate than relations that consider the variation of viscosity. Cluster theories developed for diffusion behavior near critical points were found to explain the data well only in water-organic systems on the water-rich side.
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  • 169
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    AIChE Journal 42 (1996), S. 901-909 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A process-engineering model is presented for the stratified-wavy-to-intermittent (SW-I) flow-pattern transition in slightly inclined gas-liquid pipe flow. The main parameter for predicting (in) stability of wavy flow in inclined pipes is the average liquid holdup, which was found to reach a maximum, critical value at flow-pattern transition. Observed values of the critical liquid holdup vary between 0.07 and 0.42, depending on pipe diameter, angle of inclination and transport properties of the gas-liquid system. Measurements were performed in transparent glass pipes of 26- and 51-mm dia., at ten angles of inclination (0.1° ≤ β ≤ 6.0°), using air/water and air/tetradecane (n-C14H30) systems at atmospheric pressure. Flow-pattern maps are presented for selected angles of inclination, showing excellent agreement between predicted and observed flow-pattern boundaries.
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  • 170
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    AIChE Journal 42 (1996), S. 921-926 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Random walks are used to examine dispersion between miscible fluids in one-dimensional, prefractal porous medium. Mixing in such media is anomalous and several nonlocal theories have been proposed to describe this non-Fickian characteristic. This work simulates dispersion via a random walk in a prefractal media by incorporation local and spatially nonlocal effects and compares the results with laboratory experiments. Results suggest that nonlocal models fit experimental data better than local models.
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  • 171
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    AIChE Journal 42 (1996), S. 927-931 
    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 sedimentation velocity of multiparticle suspensions was investigated experimentally for cases where the column wall is likely to have a nonnegligible effect. The experiments demonstrate that the container wall diameter influeces the falling velocity only for dilute systems, which is in contrast with a widely used, established empirical relationship.
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  • 172
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    AIChE Journal 42 (1996), S. 940-952 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It has been shown that small-amplitude oscillations can augment the diffusional flux across a cylindrical tube by several orders of magnitude through Taylor-Aris dispersion phenomena (Aris, 1960). This enhancement in mass transport is selective for species with different molecular diffusion coefficients. This article shows that by coupling fluid oscillations with a reversible absorption in a stationary phase, the transport of species, which have similar molecular diffusivities but different affinities for the stationary phase, can be enhanced selectively. We developed analytical and asymptotic solutions to the enhancement of mass transfer as a result of the interaction between reversible absorption and fluid oscillations in a cylindrical tube. These results were qualitatively confirmed by experiments with a model system. For purely oscillatory flow, the maximum selectivity (the ratio of the fluxes of the species to be separated) achievable is 4.4 for solute species with widely different affinities for the stationary phase. The superposition of a small-amplitude steady backflow, however, can greatly increase the selectivity, but at the expense of throughput. Analysis shows that this technique may offer improvements relative to conventional liquid membrane separations, if the solute affinities for the stationary phase do not greatly differ or if a thick membrane is required for stability.
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  • 173
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    AIChE Journal 42 (1996), S. 932-939 
    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 volumetric flow rate of liquid and gas through small gigaporous particles was measured by a new method that isolates single particles in a test apparatus. To our knowledge, this is the first direct confirmation of flow through gigaporous particles made at pressure drops experienced during normal operation. High-performance liquid chromatography particles from 30 to 50 μm in diameter, previously reported to exhibit convection-enhanced intraparticle mass transfer, were studied. Using a CFD model of the test system, the permeability of individual particles was determined from the pressure-drop-flow-rate relationship. The average measured permeability of the particles studied is 7.89 × 10-15 m2 with no dependence on particle size. This is 4 to 17 times greater than values calculated from models currently used to estimate the permeability of these kinds of particles. No other experimentally measured values of permeability have been reported for particles of this size. The results of this study might imply that the intraparticle structure does not behave like a bed of uniformly packed microspheres, but rather as an inhomogeneous assemblage of microparticles. The measured permeability values offer the possibility of developing better models of the intraparticle flow field under normal operating conditions. Knowledge of the intraparticle flow field is an important step in deriving predictive models of convective mass transfer in these types of particles.
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  • 174
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    AIChE Journal 42 (1996), S. 953-959 
    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 formation of a filter cake during mechanical dewatering (filtration and expression) of sludge is studied using one-dimensional nuclear magnetic resonance (NMR) imaging of porosity profiles. The experiments clearly showed the formation of a porosity gradient during filtration and the disappearing of this gradient during expression, forming a cake with a uniform porosity. This technique makes it possible to investigate the material behavior of the porous medium, which is needed before any model calculations can be performed. The results indicate that NMR imaging is useful in nondestructive monitoring of the filtration and expression process of sludge.
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  • 175
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    AIChE Journal 42 (1996), S. 960-972 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Sedimentation and consolidation of suspensions of fine particles were analyzed by integrating experimental measurement of properties in a centrifuge with a comprehensive numerical model. The yield stress and settling velocity for tailings from tar sands extraction were determined experimentally as a function of the volume fraction of solids. The evaluated state functions were used to simulate batch settling and consolidation, and the results compare well with long-term settling tube tests. This approach is very attractive where gravity sedimentation may take many years, and it allows prediction of the rate of clear water production, total time for sedimentation and consolidation, and the maximum concentration of solids.Scaling of the sedimentation between centrifuge and field conditions is discussed. Conversion of permeability-void ratio relationships from geotechnical experiments to state functions of hindered settling velocity is demonstrated, allowing the use of data derived from a variety of experimental techniques.
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  • 176
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    AIChE Journal 42 (1996), S. 973-982 
    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 that makes it possible to evaluate the secondary nucleation rate in a pilot-scale industrial crystallizer is presented. It relates the secondary nucleation rate directly to the volume rate of attrition of large parent crystals. Two other terms are included in the equality, one that expresses the distribution formed by the attrition fragments, and the other that expresses a survival efficiency accounting for the percentage of attrition fragments that grow out after the attrition step. The model is further tested on a 970-L draft-tube-baffled evaporative crystallizer with ammonium sulfate as the model material used for crystallization and having an on-line crystal size-distribution measuring device.
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  • 177
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    AIChE Journal 42 (1996), S. 995-1009 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Detecting out-of-control status and diagnosing disturbances leading to the abnormal process operation early are crucial in minimizing product quality variations. Multivariate statistical techniques are used to develop detection methodology for abnormal process behavior and diagnosis of disturbances causing poor process performance. Principal components and discriminant analysis are applied to quantitatively describe and interpret step, ramp and random-variation disturbances. All disturbances require high-dimensional models for accurate description and cannot be discriminated by biplots. Diagnosis of simultaneous multiple faults is addressed by building quantitative measures of overlap between models of single faults and their combinations. These measures are used to identify the existence of secondary disturbances and distinguish their components. The methodology is illustrated by monitoring the Tennessee Eastman plant simulation benchmark problem subjected to different disturbances. Most of the disturbances can be diagnosed correctly, the success rate being higher for step and ramp disturbances than random-variation disturbances.
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  • 178
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    AIChE Journal 42 (1996), S. 1010-1032 
    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 generalized modeling framework for process synthesis alternatives is proposed, based on fundamental mass/heat-transfer principles. A multipurpose mass/heat-transfer module is introduced as the building block of the framework, whereas basic block-superstructure rules (such as splitting, mixing, and bypassing) are used to develop a systematic representation of process units and process structures, conventional or not. Process synthesis procedures are explored within this modeling framework, where synthesis alternatives are not postulated as process unit networks, but explored simultaneously without predefining synthesis schemes, as combinations of mass/heat-exchange stream matches. The representation potential of this framework is illustrated with examples from unit operations, whereas synthesis example problems are presented to show the broad range of process alternatives that can be modeled, identified, and optimized.
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  • 179
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    AIChE Journal 42 (1996), S. 983-994 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: One of the key components in the operation of chemical plants is the ability to operate over a range of conditions while satisfying performance specifications. A method for determining the necessary open-loop backoff from a steady-state nominal optimum is introduced to ensure that disturbances cause no constraint violation. This approach consists of defining a joint optimization-flexibility problem that can be solved within an optimization framework based on an iterative procedure. By formulating the optimization problem in economic terms, the backoff in the objective function is a measurement of the open-loop economic penalty that is necessary to be paid to achieve feasible operation over the disturbance range of interest (considering the worst combination). An upper bound on the economic potential available for closed-loop control can then be established, providing a valid reference for ranking different control schemes. Three examples presented illustrate the application of this approach: (1) a simple linear example, (2) a system of two CSTRs; and (3) an industrial distillation column.
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    AIChE Journal 42 (1996), S. 1032-1032 
    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 42 (1996), S. 1033-1040 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Necessary and sufficient conditions for the robust stability and performance of the Smith-predictor controller, modeled under a norm-bounded uncertainty, are given in a general formulation. In addition, a practical stability condition is obtained as a special corollary of the main results. These conditions provide useful and practical guidelines for the development of a systematic robust design method. In particular, an application is developed for the robust control of first-order deadtime systems with simultaneous uncertainties in all three parameters of the model. A simulation example and the results of a case study on the robust level control of a coupled-tanks apparatus are provided for illustration.
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    AIChE Journal 42 (1996), S. 1069-1076 
    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 oxidation of asphalt is a major cause of pavement failure. The low-temperature oxidation kinetics of 14 asphalts are presented. At constant temperature and oxygen presure, asphalt oxidation occurs in two stages: (1) a relatively rapid-rate period, followed by (2) a long period of constant rate. Activation energies for the constant-rate region vary from 64 to 109 kJ/mol, and reaction orders relative to oxygen pressure vary from 0.25 to 0.61. This variation in activation energy and reaction order leads to skepticism regarding the present practices of evaluating road-condition asphalt-hardening rates at a single elevated temperature and perhaps at an elevated pressure. The asphalts occur in essentially two groups, one at high values of both activation energy and reaction order and the other at low values of each. The data indicate the existence of an isokinetic temperature near 100°C. The degree of oxidation that occurs during the initial rapid-rate region varies inversely with the oxygen reaction order of the constant-rate region.
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    AIChE Journal 42 (1996), S. 1195-1195 
    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 42 (1996), S. 1191-1194 
    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 42 (1996), S. 1195-1195 
    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 42 (1996), S. 1197-1198 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 187
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    AIChE Journal 42 (1996), S. 1195-1197 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 188
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    AIChE Journal 42 (1996), S. 1198-1199 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 189
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    AIChE Journal 42 (1996), S. 1200-1200 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 190
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    AIChE Journal 42 (1996), S. 1201-1212 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Atomization experiments, motivated by the need to suppress misting of machining oils, were conducted on dilute solutions of polyisobutylene (PIB) in mineral oil using a coaxial air blast atomizer and an optical (Fraunhofer diffraction) particle sizer. Polymer concentrations (0.1 to 1.0 kg/m3) and molecular weight (1.0 to 2.2 million) were varied to determine their effects on aerosol drop-size distributions. The pure oil and PIB - oil solutions were atomized at air/liquid mass ratios near 10 and atomizing air velocities of 150-270 m/s, producing droplet-size distributions with mass mean diameters (MMD) in the range of 7-15 μm for the pure oil. Under identical atomization conditions, the MMDs of PIB solutions were 20-200% higher than pure oil. These observed increases in MMD correspond to significant reductions in the fraction of droplets falling below 5 μm in diameter that constitute the misting problem in industrial machining applications. Observed effects of PIB on atomization are ascribed to the viscoelastic properties of PIB - oil solutions as characterized by the elongational viscosity ηE. This relationship is examined by correlating the change in MMD caused by PIB addition with the stress-dependent elongational viscosity of PIB-oil solutions as predicted by the FENE-P dumbbell kinetic theory. The increase in MMD due to PIB varies linearly with the predicted ηE at constant atomization tensile stress.
    Additional Material: 15 Ill.
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  • 191
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    AIChE Journal 42 (1996) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 192
    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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  • 193
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    AIChE Journal 42 (1996), S. 1213-1219 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Rosensweig's (1979) analysis of the stability of gas-fluidized magnetically stabilized fluidized beds (MSFBs) with voidage perturbations is modified to include terms dependent on the fluid density. This allows the stability analysis to be applicable to liquid-fluidized MSFBs, which have potential use in liquid chromatography. Results show that in systems where the fluid density is not insignificant when compared to the solid-phase density, the difference in density between the two phases should be used when normalizing the magnetization required to achieve stability. Comparisons between theory and experiment show that although the present analysis improves on Rosensweig's analysis, it still does not give reliable, quantitative predictions of stability behavior. It is suggested that for liquid-fluidized MSFBs, stability to particle velocity perturbations, rather than to voidage perturbations, is more relevant to chromatographic applications wherein the purpose of magnetic stabilization is to prevent particle mixing as opposed to preventing the occurrence of bubbling and slugging observed in gas-fluidized beds.
    Additional Material: 4 Ill.
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  • 194
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    AIChE Journal 42 (1996), S. 1220-1224 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new technique was developed to measure the hydraulic permeability of reinforced gel membranes and allows calculation of the Darcy permeability (κ) of the gel. It was applied to agarose with concentrations ranging from 2.0 to 7.3%. To create membranes that would be thin enough to yield easily measured filtration rates at modest applied pressures and yet withstand handling, gels were cast on woven polyester meshes. The resulting membranes had thicknesses of 70-100 μm and a fractional open area of 0.32. To correct for the presence of the mesh, finite-element solutions were obtained for the pressure field in the 3-D region occupied by the gel. For the meshes used here, the hydraulic permeability of the reinforced membrane was calculated to be 0.47-0.55 times that for a layer of pure gel, the exact value depending on the thickness of the composite membrane. The principal determinant of κ was the agarose concentration, but there was a secondary effect of applied pressure. The Darcy permeability extrapolated to zero applied pressure (κ0) varied from 616 nm2 for 2.0% agarose to 22 nm2 for 7.3% agarose. At a given gel concentration, the value for κ0 was as much as twice the value for κ measured at the maximum pressure difference of 20 kPa. This method can be adapted to a variety of other gel materials.
    Additional Material: 4 Ill.
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  • 195
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    AIChE Journal 42 (1996), S. 1225-1233 
    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 theoretical model for the prediction of drop and bubble (fluid-particle) breakup rates in turbulent dispersions was developed. The model is based on the theories of isotropic turbulence and probability and contains no unknown or adjustable parameters. Unlike previous work, this model predicts the breakage rate for original particles of a given size at a given combination of the daughter particle sizes and thus does not need a predefined daughter particle size distribution. The daughter particle size distribution is a result and can be calculated directly from the model. Predicted breakage fractions using the model for the air-water system in a high-intensity pipeline flow agree very well with the available 1991 experimental results of Hesketh et al. Comparisons of the developed model for specific particle breakage rate with earlier models show it to give breakage-rate values bracketed by other models. The spread in predictions is high, and improved experimental studies are recommended for verification.
    Additional Material: 7 Ill.
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  • 196
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    AIChE Journal 42 (1996), S. 1234-1243 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The transport of water and pentane vapor in Langmuir-Blodgett (LB) films of arachidic acid is investigated. A quartz crystal microbalance is used to monitor the mass increases of the films upon exposure to the vapor as a function of the pressure. By examining films of different thicknesses, it is shown that it is possible to measure both surface adsorption and solubility. Diffusivity is calculated from the rate of uptake. Water and pentane have Fickian diffusion coefficients of 4 × 10-12 cm2·s-1 and 1 × 10-12 cm2·s-1, respectively. The effect of both aging and annealing of the LB films on the vapor uptake is studied and it is shown that the uptake is sensitive to the state of the film.
    Additional Material: 10 Ill.
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  • 197
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    AIChE Journal 42 (1996), S. 1263-1276 
    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 demulsification techniques investigated use preferential surface wetting to allow separation of oil and water phases in ultrafiltration and microfiltration membranes. A hydrophobic membrane allows the permeation of an oil phase at almost zero pressure and retains the water phase, even though the molecular weight of the water molecule (18) is much smaller than that of the oil molecule (198 for tetradecane, used in this study). Hydrophobic membranes having pore sizes from 0.02 to 0.2 μm were tested for demulsification of water-in-oil emulsions and water/oil/solid mixtures. The dispersed (aqueous)-phase drop sizes ranged from 1 to 5 μm. High separation rates, as well as good permeate quality, were obtained with microfiltration membranes. Water content of permeating oil was 32-830 ppm depending on operating conditions and interfacial properties. For emulsions with high surfactant content, simultaneous operation of a hydrophobic and hydrophilic membrane, or simultaneous membrane separation with electric demulsification was more efficient in obtaining complete phase separation.
    Additional Material: 10 Ill.
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  • 198
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    AIChE Journal 42 (1996), S. 1244-1262 
    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 generalized parallel pore and surface diffusion model for multicomponent adsorption and liquid chromatography is formulated and solved numerically. Analytical solution for first- and second-order central moments for a pulse on a plateau input is used as benchmarks for the numerical solutions. Theoretical predictions are compared with experimental data for two systems: ion-exchange of strontium, sodium, and calcium in a zeolite and competitive adsorption of two organics on activated carbon. In a linear isotherm region of single-component systems, both surface and pore diffusion cause symmetric spreading in breakthrough curves. In a highly nonlinear isotherm region, however, surface diffusion causes pronounced tailing in breakthrough curves; the larger the step change in concentration, the more pronounced tailing, in contrast to relatively symmetric breakthroughs due to pore diffusion. If only a single diffusion mechanism is assumed in analyzing the data of parallel diffusion systems, a concentration-dependent apparent surface diffusivity or pore diffusivity results; for a convex isotherm, the apparent surface diffusivity increases, whereas the apparent pore diffusivity decreases with increasing concentration. For a multicomponent nonlinear system, elution order can change if pore diffusion dominates for a low-affinity solute, whereas surface diffusion dominates for a high-affinity solute.
    Additional Material: 13 Ill.
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  • 199
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    AIChE Journal 42 (1996), S. 1304-1318 
    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 critical decisions must be made in the charging sequence of batch reactors: target setting and alarm generation. A number of statistics-based strategies are proposed in this article to perform these tasks. The off-line and on-line target setting procedures developed in this work can be adopted to increase the profit margin of any given batch process without sacrificing reliability. A synthesis method for building optimal alarm logic is also described in detail. Monitoring systems constructed according to this suggested approach are effective in reducing the probability of undetected faulty batches. Extensive simulation studies show that the proposed strategies are suitable for application of manufacturing high-value-added products, which is a prevailing practice in batch processes.
    Additional Material: 4 Ill.
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  • 200
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    AIChE Journal 42 (1996), S. 1319-1325 
    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-situ laser reflectance monitoring of metal-organic chemical vapor deposition (MOCVD) is an effective way to monitor growth rate and expitaxial layer thickness of a variety of III-V and II-VI semiconductors. Materials with low optical extinction coefficients, such as ZnTe/GaAs and AlAs/GaAs for a 6328 Å HeNe laser, are ideal for such an application. An Extended Kalman filter modified to include a variable forgetting factor was applied to the MOCVD systems. The filter was able to accurately estimate thickness and growth rate while filtering out process noise and cope with sudden changes in growth rate, reflectance drift, and bias. Due to the forgetting factor, the Kalman filter was successful, even when based on very simple process models.
    Additional Material: 10 Ill.
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