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  • 1995-1999  (418)
  • 1985-1989  (658)
  • 1997  (418)
  • 1985  (658)
  • Chemical Engineering  (1,076)
  • 101
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2123-2132 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Renaturation of protein expressed as inclusion bodies within Escherichia coli is a key step in many bioprocesses. Operating conditions for the refolding step dramatically affect the amount of protein product recoverd, and hence profoundly influence the process economics. The first systematic comparison of refolding conducted in batch, fed-batch and continuous stirred-tank reactors is provided. Refolding is modeled as kinetic competition between first-order refolding (equilibrium reaction) and irreversible aggregation (second-order). Simulations presented allow direct comparison between different flowsheets and refolding schemes using a dimensionless economic objective. As expected from examination of the reaction kinetics, batch operation is the most inefficient mode. For the base process considered, the overall cost of fed-batch and continuous refolding is virtually identical (less than half than of the batch process). Reactor selection and optimization of refolding using overall economics are demonstrated to be vitally important.
    Additional Material: 10 Ill.
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  • 102
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2141-2145 
    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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  • 103
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2146-2147 
    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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  • 104
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2148-2152 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 105
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 106
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2153-2156 
    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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  • 107
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2180-2186 
    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 comprehensive one-dimensional fully coupled hydrodynamic treatment of the film profiles behind liquid slugs in horizontal and inclined gas-liquid slug flow is presented. Experiments were performed in horizontal air-water pipes 32 and 50 mm in diameter, the smaller also being inclined to an angle of 5 degrees. Time traces of film thickness were produced with the use of a wire-probe technique. The experimental results are compared against the theory presented here, as well as previously reported hydrodynamic models. It is concluded that the film profiles calculated by the use of one-dimen-sional models are highly sensitive to the choice of input variables, for example, the slug translational velocity; however, good agreement is achievable provided that consistent hydrodynamic equations and correct input variables are used. It is hoped that the work presented here will influence future mechanistic models of slug flow.
    Additional Material: 9 Ill.
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  • 108
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2194-2202 
    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 field in a standard mixing reactor with a Rushton impeller is analyzed by using techniques from the theory of nonlinear dynamical systems. It is shown that the dynamical behavior contains a quasi-periodic motion with three frequencies, fp, the frequency associated with the rotation of blades, fp/6, and a third frequency f'. Relying on an evaluation of the correlation dimension equal to 3.9, the phase space is likely to be at least four-dimensional. Moreover, a set of four ordinary differential equations is indeed automatically obtained by using a global vector field reconstruction technique, confirming the existence of a 4-D-deterministic behavior contributing to the dynamics of the system.
    Additional Material: 15 Ill.
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  • 109
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2227-2238 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: During process design of reactive distillation systems, there is often uncertainty in the value of the reaction equilibrium constant (Keq), whether it is determined experimentally or calculated from thermochemical data. The effect of the reaction equilibrium constant on the existence and location of reactive azeotropes (constant boiling reactive mixtures) is explored for chemical equilibrium systems with a single chemical reaction. With a known set of starting points, arc-length continuation was used to track solutions of the equations for reactive azeotropy as a function of the reaction equilibrium constant. The results, portrayed in bifurcation diagrams, reveal that azeotropes may appear or disappear as the equilibrium constant is varied. Results for the esterification of acetic acid with ethanol indicate three distinct regions of phase behavior. The first regime (Keq 〈 0.449) contains a quaternary saddle reactive azeotrope. At intermediate values of the reaction equilibrium constant (0.449 〈 Keq 〈12.5), there are no reactive azeotropes in the system. In the third regime (Keq 〈 12.5), a minimum-boiling quaternary reactive azeotrope appears. In addition, for three reported literature values of the reaction equilibrium constant, each one lies in a different regime. Other examples also illustrate the broad taxonomy of reactive azeotropic systems.
    Additional Material: 18 Ill.
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  • 110
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2239-2245 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The separation performance of binary hydrogen sulfide-hydrogen mixtures by a nanoporous carbon membrane called selective surface flow (SSF) membrane is described. The membrane selectively permeates H2S from H2, and a H2-enriched stream is produced at the feed-gas pressure. A two-stage embodiment of the SSF membrane is described for production of high-purity H2 with high H2 recovery from an equimolar H2S-H2 feed gas. A novel protocol for operation of the two-stage membrane is needed to achieve that separation goal.
    Additional Material: 5 Ill.
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  • 111
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2289-2299 
    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 competition between heuristic and optimization approaches for process synthesis and process operations problems has caused major controversy in recent years. Heuristics offer fast solutions but no guarantee of optimality. Mathematical programming approaches, on the other hand, offer rigor but suffer from combinatorial explosion of computational requirements. The use of analytical investigations is proposed as a theoretical means to characterize the behavior of heuristics and optimization algorithms and produce a framework that combines the strengths of the two approaches while eliminating their weaknesses. The approach contrasts and complements the current practice in process systems engineering, which is entirely empirical in nature. The proposed paradigm is demonstrated in the context of the multiperiod capacity expansion problem for chemical process networks, a problem having much in common with both process synthesis and operations problems. Analytical investigations for this problem lead to the development of a heuristic that is proved to be asymptotically optimal under standard assumptions about the problem parameters. In the more general context of process synthesis and operations, analytical investigations present a large array of opportunities.
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  • 112
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2903-2910 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To evaluate the effect of viscoelasticity on bubble formation, four rheological parameters of viscoelastic liquids were defined and measured by a rheometer. The effects of operating conditions and concentration of polyacrylamide aqueous solutions (PAA) as viscoelastic liquids on bubble volume and the growth curve were experimentally measured. A high-speed video camera showed that the shapes of a bubble growing in vis-coelastic liquids are not spherical. In this study, a nonspherical bubble formation model was proposed to theoretically estimate the volume, shape and growth curve of bubbles formed from an orifice submerged in viscoelastic liquids which are assumed to follow Maxwell's viscoelastic model. This experimental results in relatively low concentrations of PAA, as well as previous researchers' results, agreed relatively well with the calculated ones by this model.
    Additional Material: 14 Ill.
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  • 113
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2944-2947 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: New correlations, based on the rough hard-sphere theory and an extensive literature database, were developed for the determination of the binary diffusion coefficients of liquid and solid solutes in supercritical solvents. The correlations were tested to predict 107 solute-solvent systems with good results. The input data required for the correlations are the solute molecular weight, temperature, density and the solvent basic properties (molecular weight, critical volume, and critical pressure).
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  • 114
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 268-272 
    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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  • 115
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 339-344 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental investigation was conducted to determine the boiling heat-transfer characteristics in a thermosyphon condenser-reboiler of air-separation plants. The test section was a plate-fin heat exchanger of practical size of 0.106 m width and 2.56 m length. The testing fluid was nitrogen. Experiments were carried out within a range of pressure from 150 to 300 kPa, submergence from 1.95 to 2.80 m, and heat flux up to 11 kW/m2 under constant wall-temperature condition. The liquid superheat at the onset of boiling was rather significant. The boiling heat-transfer coefficients obtained agreed well with Chen's correlation modified by Colburn's J factor within a mean deviation of 9.3%.
    Additional Material: 7 Ill.
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  • 116
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 363-373 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Batchwise fluidized-bed calcination and sulfation of a limestone were done to investigate particle comminution phenomena and their relation with parallel occurrence of reactions. Operating conditions of the bed were those typical of atmospheric bubbling fluidized-bed combustors. A general framework of comminution phenomena is outlined, which includes different types of fragmentations as well as attrition by abrasion. Comminution processes were characterized by following the modifications of bed sorbent particle-size distribution and the elutriation rates of fines throughout conversion. Mutual interactions between comminution processes and the progress of chemical reactions are assessed.
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  • 117
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1171-1179 
    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 theoretical approach is proposed for the yield stress of concentrated, flocculated particulate suspensions. Explicit cognizance is taken for the three-dimensional, mechanically rigid particle network held together by interparticle forces wherein the mean coordination number in the assemblage increases and the separation between the particles decreases with an increase in the volume fraction of the solid phase. The Rump-Molerus model relting isotropic normal stress and isotropic normal interparticle force in a bed of single-sized spheres is modified to incorporate the size distribution of particles and extended to the suspension network. The model estimates the yield stress as a function of solids loading for various kinds of size distribution and is in reasonable agreement with experimental data when the surface properties of the particle are held constant.
    Additional Material: 11 Ill.
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  • 118
    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 low-temperature oxidation chemistry of linear and branched alkanes is discussed with the aim of unifying their complex behavior in various experimental systems using a single detailed kinetic model. New experimental data, obtained in a pressurized flow reactor, as well as in batch- and jet-stirred reactors, are useful for a better definition of the region of cool flames and negative temperature coefficient (NTC) for pure hydrocarbons from propane up to isooctane. Thermochemical oscillations and the NTC region of the reaction rate of the low-temperature oxidation of n-heptane and isooctane in a jet-stirred flow reactor are reproduced quite well by the model, not only in a qualitative way but in terms of the experimental frequencies and intensities of cool flames. Very good agreement is also observed for fuel conversion and intermediate-species formation. Irrespective of the experimental system, the same critical reaction steps always control these phenomena. The results contribute to the definition of a limited set of fundamental kinetic parameters that should be easily extended to model heavier alkanes.
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  • 119
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1309-1318 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The substitution reaction of hexachlorocyclotriphosphazene, N3P3Cl6, with phenol was performed to synthesize the partially substituted (phenoxy) chlorocyclotriphosphazenes, N3P3Cl6 - i(OC6H5)i, i = 1 - 6 by phase-transfer catalysis (PTC) in an organic phase/alkaline solution. The steric hindrance effect plays a crucial role in this reaction. The reaction system was controlled by both chemical kinetics and mass-transfer effects. The mass transfer of the catalyst between two phases was investigated by a pseudosteady-state liquid-liquid PTC (LLPTC) model. Also, the intrinsic reaction-rate constants of the series substitution and the overall mass-transfer coefficient of the catalyst from the organic phase to the aqueous phase were determined by a combined model. In addition, the corresponding energies, enthalpies, and entropies of activation of the series substitution were also estimated.
    Additional Material: 7 Ill.
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  • 120
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    AIChE Journal 43 (1997), S. 1357-1361 
    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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  • 121
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    AIChE Journal 43 (1997), S. 1390-1402 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Liquid circulation in bubble columns influences many system properties such as mass transfer and catalyst dispersion. Conditions favorable for liquid circulation often exist only for highly turbulent slurries. Experiments under conditions of lowered surface tension proved conclusively that uniform circulation can exist even in the bubbly-flow regime. Moreover, the measured circulating velocity profile is more plug-shaped in the center core than traditional models, which take a parabolic shape. These observations led to the application of a circulation theory based on an energy-dissipation model for turbulent eddy viscosity, which can be easily computed as a simple function of superficial-gas velocity. Two length scales were used in model calculations depending on flow regime: bubble diameter for bubbly flow and column diameter for churn turbulence. The liquid-velocity profile contained a tuned dimensionless proportionality constant, which resulted in two different average values, k = 2.51 for bubbly flow and 0.0242 for churn turbulence, when tuned to experimental data. The integral average eddy viscosity is numerically equivalent to the eddy dispersion coefficient for bubbly flow. Predicted liquid velocity compared very favorably with new measured values under conditions of low surface tension and with literature values.
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  • 122
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1436-1447 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Droplet breakup in laminar flows is important in emulsification processes and polymer blending. The influence of surfactants on droplet deformation and breakup in a plane hyperbolic flow was studied experimentally in an opposed-stream device. As in the case of simple shear flow, the inhomogeneity of the surfactant distribution along the droplet interface has a pronounced effect. Our results are qualitatively consistent with other numerical studies for droplet breakup in an axisymmetric elongational flow. Also a striking similarity is noted with other experimental observations for the deformation and breakup of polymeric drops in a quasi-steady-plane hyperbolic flow. The critical capillary number for droplet breakup in the experiments correlates with the interfacial viscoelasticity, and a reformulation of the numerical framework in terms of interfacial elasticity parameters is suggested for future numerical work including other linear flows.
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  • 123
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    AIChE Journal 43 (1997), S. 1448-1457 
    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 revised machine learing methodology is applied to a simulated crystallization process flowsheet for continual imporvement of its performance by generating and analyzing process data. The aim is to identify bands of crucial decision variables leading to zones of best average process performance. The methodology comprises two components: symbolic induction and case-based reasoning. It uses an incremental algorithm to update performance classification rules, which not only improves the efficiency of the symbolic induction of the classification rules by eliminating the need for their periodic reinduction, but also simplifies the case-based reasoning step. The new concepts and procedures are illustrated by application to a potassium nitrate crystallization process comprising a mixed-suspension, mixed-product-removal crystallizer, a hydrocyclone, and a fines dissolver, By identifying and establishing ranges for the most crucial decision variables, namely, feed concentration, flow rate, and cooling stream temperature, three zones leading to an improvement of nearly 12% on nominal average performance are detected within two generations of the classification rules.
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  • 124
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    AIChE Journal 43 (1997), S. 1559-1568 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Thermochemical data of mineral oil fractions are scarce. Due to the complex structure of natural hydrocarbon mixture, standard heat and Gibbs free energy of formation depend on the sample. A procedure for predicting these properties is presented. Both properties depend on the hydrocarbon type and on its molecular weight. The double-bond equivalent (DBE) and the number of olefinic double bounds are the important characterization parameters of the model. DBE can basically be calculated from molecular weight and elemental composition. Alternatively, boiling point and atomic H/C ratio can be used if the model is applied to mineral oil fractions from which boiling curves can be obtained. A criterion for testing the reliability of the estimated DBE value is available, because DBE is also a function of structural group distribution.The relevance of the DBE concept is shown with regard to hydroprocessing of mineral oil fractions. The model can be applied to total average molecules as well as to an arbitrary number of pseudocomponents and continuous mixtures. The difference between feed and product DBE is equivalent to the amount of hydrogen consumed for hydrogenation of unsaturated hydrocarbons. Further properties of the product can be predicted.
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  • 125
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    AIChE Journal 43 (1997), S. 1569-1578 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: For the first time, a model for dynamic adsorption and tension of diffusion-controlled systems has been extended to binary premicellar mixtures of nonionic surfactants of different adsorption capacities and nonideal interactions in the monolayer. Local equilibria between subsurface concentrations and adsorbate densitities are modeled using the nonideal adsorbed solution theory, which describes these two elements. The model shows that larger molecules (those with the smaller adsorption capacity) tend to be preferentially adsorbed at low times, if they have equal adsorption equilibrium constants and diffusivities, and smaller moleules at longer times. This adsorption selectivity is reduced when larger molecules have a much larger adsorption equilibrium constant, or when there are negative deviations from ideality in the monolayer. This model's predictions are compared to tension data for two nonionic surfactants, C12E5 and Triton X-100, at 25°C. The data are represented well by the diffusion-controlled model with a finite diffusion-layer thickness, which describes the faster decrease in tension observed with the bubble surfactometer, compared to data with other techniques. With this model, surface coverages and concentration profiles are calculated, thus elucidating the adsorption selectivity of molecules of different adsorption capacities. Synergistic effect in dynamic tension and adsorption can be predicted. Mild synergism in dynamic tension lowering by the preceding nonionic surfactants is also observed.
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  • 126
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    AIChE Journal 43 (1997), S. 1597-1604 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Hartree-Fock theory and density functional theory were used to compute the enthalpy and entropy changes of dimerization for a number of hydrogen-bonding compounds. In Part 1, the calculational methods and procedures use for the water dimer are described, and the results obtained are compared with those of others and with experimental estimates in the literature. Here, a variety of organic compounds that can self associate and/or cross associate are considered. The results obtained for the self-association of these compounds are compared with estimates obtained from various types of experimental data. The results are also used to examine the validity of group-contribution methods for hydrogen-bonding mixtures and to test a simple estimation procedure for cross dimerization that can reduce the number of calculations, such as those described here, that need to be done.
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  • 127
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    AIChE Journal 43 (1997), S. 1611-1626 
    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 comprehensive composite database for distillation sieve-tray efficiency is used to develop point efficiency and entrainment correlations based on a model that considers the fluid on the distillation tray to be contained in a liquid-continuous region near the tray deck and a vapor-continuous region on top of the liquid-continuous region. This model allows estimates of the portion of the mass transfer that occurs in each region and the mass-transfer resistance that occurs on the liquid side and vapor side of the interface. For most cases, most of the mass transfer occurs within the liquid-continuous region. The liquid side resistance is often significant.The entrainment correlation is consistent with the work of Bennett et al., which relates entrainment to the ratios of the liquid to vapor density and the froth height to the tray spacing. A simple liquid continuous-only mass-transfer model containing only four empirical parameters correlates the point efficiency data to within 6.4%. Despite a twofold change in vapor Schmidt number, no dependency on vapor Schmidt number is seen. Important dimensionless groupings are the Reynolds number based on the hole velocity, effective froth density, ratio of the liquid inventory to the perforation diameter, and fraction of the tray area perforated. Mathematically simple and accurate methods allow the prediction of the section efficiency for trays operating in cross or parallel flow. They address vapor and liquid mixing, entrainment and a criterion to avoid significant degradation of the tray efficiency due to weeping.
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  • 128
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    AIChE Journal 43 (1997), S. 1641-1648 
    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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  • 129
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    AIChE Journal 43 (1997), S. 1649-1651 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 130
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    AIChE Journal 43 (1997), S. 1653-1661 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pulsed magnetic field gradient stimulated echo NMR measurements are performed for diffusion and flow of an aqueous phase both within a sample of packed spherical beads and within a 25% porosity Fontainebleau sandstone. The stimulated echo dependence on the gradient pulse area q is used to derive the displacement probability distributions PΔ(X) for fixed observation times Δ. The shape of PΔ(X) as a function of Δ is simulated for computer-generated porous media, and a good agreement is obtained between the experimental NMR data and the simulations.
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  • 131
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    AIChE Journal 43 (1997), S. 1675-1683 
    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 gas-liquid flows through tee junctions, because of the difference in inertia between the phases, the flowing mass fractions for an individual phase at the outlet sides differ from those at the inlet. This phase separation is an important consideration in delivering fluids and energy through pipe networks in the power and process industry. In this work, air-water and steam-water flows through branching and impacting tee junctions are considered. Under certain conditions (when the volumetric fraction of the liquid drops does not change appreciably and their bulk density is much higher than the gas density, and when the flow rates and/or the gas volumetric fraction are high), these flows can be approximated as irrotational flows of incompressible, inviscid fluids and are amenable to potential flow methods, for example, conformal mapping. For the general case of gas-liquid flows through a branching or impacting tee, a CFD code is utilized to conduct transient flow simulations. Predictions of phase separation for both types of tee junction agree well with experimental data.
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  • 132
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    AIChE Journal 43 (1997), S. 1691-1699 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pore fractal objects are expected to be optimal catalysts, since material is supplied to the narrower pores, which are also shorter through the larger pores where diffusion resistance is smaller. To demonstrate this, diffusion and reaction were simulated on Sierpinski-gasket-type fractal objects and on the corresponding nonfractal uniform-pore structures of the same size, porosity and reactive area. Positive order reactions limited by Knudsen diffusion were shown to exhibit larger rates in fractal than in uniform-pore objects. Fractal catalysts also exhibited a new intermediate domain in which the rate depends only weakly on the kinetics parameters. In nonmonotomic kinetics the branching point (bifurcation point) was extremely sensitive to the pore structure.
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  • 133
    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 recovery of the acidic structure and activity during the regeneration step by coke combustion of an HZSM-5 zeolite-based catalyst used in the methanol-to-gasoline (MTG) process in reaction-regeneration cycles was studied. The reactivation kinetics (activity us. coke combustion time) was determined as a function of temperature and time on stream of the reaction step. The validity of the reactivation kinetic model was proven by using it for the simulation of the cyclic operation under conditions of catalyst partial reactivation, together with the kinetic model for the MTG process.
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  • 134
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    AIChE Journal 43 (1997), S. 1529-1544 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Almost-everywhere singular (AES) distributions, usually referred to as multifractal measures, provide an intermediate link between atomic distributions (distributions represented by a countable superposition of Dirac's delta terms) and smooth regular distributions. This article shows how AES distributions can be rigorously treated in connection with distributed-parameter models and presents closed-form expressions and/or recursive, uniformly converging approximation methods for integral transforms (Laplace and Stieltjes). In particular, exact results are obtained and discussed for linear and uniform nonlinear kinetcis and for transport schemes in the presence of continuous mixtures. The physical origin of AES distributions in real systems is also detailed.
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  • 135
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    AIChE Journal 43 (1997), S. 1819-1827 
    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 a high-temperature catalytic membrane reactor, a plug-flow reactor is combined with a gas-separative membrane. By selectively removing one of the reaction products, the reaction mixture is prevented from reaching equilibrium, and a higher conversion can be obtained. This concept is only valid for reactions that are limited by the thermodynamic equilibrium, such as the direct dehydrogenation of propane to propene. A tubular H2-selective silica membrane was characterized [αH2/C3H8 = 70-90 at 500°C] and used as the gas-separative membrane. The membrane reactor was filled with a chromia/alumina catalyst. The kinetics of the catalyst was studied. At 500°C the deactivation of the catalyst is slow, and the propene yield is almost constant for at least 10 h of operation. Under well-chosen process conditions, the propene yield is at least twice as high as the value obtained at thermodynamic equilibrium in a conventional reactor.
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  • 136
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    AIChE Journal 43 (1997), S. 1849-1860 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model developed for SiO2 deposition in porous Vycor glass using SiCl4 hydrolysis describes reaction, diffusion and evolution of the pore structure due to accumulation of the solid product. The deposition reaction is described by transient heterogeneous kinetics in terms of the concentrations of silanol and chloride groups in the product layer as well as those of the gaseous reactants. For typical deposition conditions the pseudo steady-state approximation for surface species could lead to erroneous predictions. Pore structure evolution is modeled by incorporating results of percolation theory. For this purpose the porous glass is represented by a Bethe lattice with coordination number 3 and alternatively by a decorated Bethe lattice in which each bond is replaced by a composite bond consisting of two bonds in series. The second network can capture the effect of pore radius variation along a single pore. For the decorated lattice, pore connectivity interruption at a higher void fraction leads to thinner deposits and shorter deposition times for pore plugging compared to the corresponding ones for the simple lattice.
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  • 137
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    AIChE Journal 43 (1997), S. 1589-1596 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To reduce the number of adjustable parameters that appear in the thermodynamic modeling of hydrogen-bonding fluids, the use of ab-initio molecular orbital calculations in the form of Hartree-Fock and density functional theories to compute thermodynamic properties are considered. In particular, the enthalpy and entropy changes on hydrogen bonding for water are computed. The theory, the computational methods and the basis sets used, as well as the results for water, are discussed. The results obtained are compared with those of others and with experimental estimates from the literature to determine the validity of the methods that are then used in this extended study. The results obtained here are also used to examine the validity of mixture group contribution results obtained here are also used to examine the validity of mixture group contribution methods for hydrogen-bonding mixtures, to develop simple estimation procedures for model parameters, and to reduce the number of calculations such as those as those described that need to be done.
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  • 138
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    AIChE Journal 43 (1997), S. 1605-1610 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method is presented for a relatively accurate, noniterative, computationally efficient calculation of high-pressure fluid-mixture equations of state, especially targeted to gas turbines and rocket engines. Pressures above 1 bar and temperatures above 100 K are addressed. The method is based on curve fitting an effective reference state relative to departure functions formed using the Peng-Robinson cubic state equation. Fit parameters for H2, O2, N2, propane, methane, n-heptane, and methanol are given.
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  • 139
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    AIChE Journal 43 (1997), S. 1627-1636 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Supercritical water oxidation of isopropyl alcohol was investigated in a pilot-scale reactor. A computational fluid-dynamics model developed reveals the detailed flow field, chemical-component distribution, temperature distribution, and salt-particle trajectories in the reactor flow domain. The near-wall fluid temperature from the numerical analysis was compared with experimental temperature data. The temperature comparison was within a 3% error band. The effect of the chemical kinetic rate was investigated for four different rates. Turbulent salt-particle trajectories were also calculated to investigate the effect of particle sizes on salt deposit on the wall. Also, a method of calculating the adiabatic reaction temperature was developed to estimate reaction temperatures prior to a full numerical simulation.
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  • 140
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    AIChE Journal 43 (1997), S. 1637-1640 
    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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  • 141
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    AIChE Journal 43 (1997), S. 1727-1736 
    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 magnitude and direction of the ultrasonic radiation forces that act on individual particles in a standing-wave field were determined using a microscope-based imaging system. The forces are calculated from measured particle velocities assuming that the drag force, given by Stokes' law, is exactly counterbalanced by the imposed ultrasonic forces. The axial primary radiation force was found to vary sinusoidally with axial position and to be proportional to the local acoustic energy density, as predicted by theory. The magnitude of the transverse primary force was determined by two independent methods to be about 100-fold weaker than the axial force. Separation concepts exploiting the transverse force for cell retention have been successful despite the great disparity in magnitude between the axial and transvers-force components. This may be explained by the reduced hydrodynamic forces on aggregated particles in transverse flow due to their alignment in the sound field.
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  • 142
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    AIChE Journal 43 (1997), S. 811-817 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Results from steady and unsteady, two-dimensional simulations of tertiary current distributions at and below the limiting current density are presented. The simulations are based on dilute-solution theory, with coupling of the concentrations of the ionic species through the electrical field. The electrical field is calculated from the electroneutrality constraint. Results confirm and extend previous theoretical predictions of the electricalmigration enhancement of the limiting current. To demonstrate the potential utility of general current-distribution solvers, measured temporal variations of the rate of copper deposition in the presence of an oscillating shear flow are measured and simulated. Experiments agree well with simulations.
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  • 143
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Transvascular and interstitial fluid movements are involved in many important biological processes such as convective macromolecular transport and contribute to the mechanical behavior of tissue. Although intimately coupled, there is a tendency in the literature to regard these two fluid-transport mechanisms separately; if the interaction is considered, the description is usually confined to the local level (e.g., transvascular or interstitial perivascular). A general framework presented here combines transvascular and interstitial fluid movement with the mechanics of soft tissue and integrates macro-and microscopic views of the phenomena. On the macroscopic level, interstitial fluid transport is described by adapting the field equations of the poroelastic theory using average field variables defined on a scale of several blood vessel diameters (∼ 1 mm), while transvascular transport is described by a generalized Starling's law. As an example, the model equations have been specialized for a spherical solid tumor and an analytical solution is presented for the transient redistribution of interstitial fluid following a rapid change in vascular pressure or flow. The model describes the overall average profiles of the interstitial fluid pressure and velocity, as well as the dilatation, displacement and stress of the solid matrix. Moreover, on a smaller length scale the model can describe the local fluid movement (perivascular) using the average field variables as boundary conditions. The basic theory provides new insight into understanding the fluid transport in biological tissues and a valuable tool for determining relevant fluid-transport parameters. Implications for improving drug delivery to solid tumors are also discussed.
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  • 144
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    AIChE Journal 43 (1997), S. 853-869 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Numerous experimental investigations on the vertical transport of dense gas-solid suspensions indicate that particles tend to segregate toward the tube wall. Although models based on the kinetic theory analogy can predict such patterns for perfectly elastic particle-particle collisions, the predictive ability of these models breaks down for inelastic collisions. In the present effort, a mathematical model is developed that incorporates two mechanisms that give rise to the lateral segregation of solids: interactions associated with individual particles based on a kinetic theory treatment and interactions associated with collections of particles based on an analogy with single-phase turbulent flows. Although these two mechanisms have been treated independently by previous workers, their combined contributions to the overall flow behavior have not been thoroughly investigated. The effect of such a treatment on the sensitivity of the model predictions to the inelasticity of particle-particle collisions is explored. A key element in eliminating the undue sensitivity appears to be a consideration of the effects associated with the collective motion of particles on the kinetic theory expressions. The resulting model can predict the expected segregation patterns for systems characterized by inelastic collisions, as well as many of the other salient features of vertical gas-solid flows.
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  • 145
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    AIChE Journal 43 (1997), S. 1921-1922 
    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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  • 146
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    AIChE Journal 43 (1997), S. 2368-2372 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 147
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    AIChE Journal 43 (1997), S. 2535-2545 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Model predictive control is used extensively to control continuous-process systems. Application of a shrinking horizon model predictive control strategy is used to predict and control the end product quality of composite laminates produced by batch autoclave curing. The main contribution is the demonstration, using a laboratory-scale autoclave, of the feasibility and advantages of a control strategy that adjusts the batch recipe on-line to correct for unmeasured disturbance: entering the process. Readily available, on-line secondary measurements are used in conjunction with the process model to predict (and hence control) quality-related end product properties. On-line monitoring is also used to monitor the process even after the possibility of on-line correction has passed. The results show that this approach significantly reduces end product quality variance.
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  • 148
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    AIChE Journal 43 (1997), S. 2405-2414 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dilute suspensions of neutrally buoyant, uniform-diameter spheres in a viscous liquid are sampled through pores in the wall of a stirred tank. These studies are performed to investigate screening effects near the sampling orifice that cause samples to be deficient in solids. The ratio of sphere concentration in the sample to that of the original suspension ranges from 0.08 to 1.12. Sample concentration decreases with decreasing sampling pore diameter and increasing stirring rates. The objectives of this work are both to obtain experimental relationships and to develop predictive techniques relating flow fields to sample concentration.Sample concentration is predicted by calculating particle trajectories in the region near the pore and by accounting for steric exclusion. Particle trajectories can differ from fluid streamlines due to lift forces generated in the flow field. These estimates constitute a priori predictions, since they do not rely on or introduce any empirical parameters. Predicted values of sample concentrations agree closely with data.
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  • 149
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    AIChE Journal 43 (1997), S. 2432-2445 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The phase holdups and the heat-transfer behavior were studied experimentally in three-phase fluidized beds over a pressure range of 0.1-15.6 MPa. Bubble characteristics in the bed are examined by direct flow visualization. Pressure effects on the bubble coalescence and breakup are analyzed mechanistically. The study indicates that the pressure affects the hydrodynamics and heat-transfer properties of a three-phase fluidized bed significantly. The average bubble size decreases and the bubble-size distribution becomes narrower with an increase in pressure. The bubble-size reduction leads to an increase in the transition gas velocity from the dispersed bubble regime to the coalesced bubble regime, an increase in the gas holdup, and a decrease in the liquid and solids holdups. The pressure effect is insignificant above 6 MPa. The heat-transfer coefficient between an immersed surface and the bed increases to a maximum at pressure 6-8 MPa and then decreases with an increase in pressure at a given gas and liquid flow rate. This variation is attributed to the pressure effects on phase holdups and physical properties of the gas and liquid phases. A mechanistic analysis revealed that the major heat-transfer resistance in high-pressure three-phase fluidized beds resides in a liquid film surrounding the heat-transfer surface. An empirical correlation is proposed to predict the heat-transfer coefficient under high-pressure conditions.
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  • 150
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    AIChE Journal 43 (1997), S. 3223-3231 
    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 standard industrial process for the purification of natural gas is to remove acid gases, mainly hydrogen sulfide and carbon dioxide, by the absorption and reaction of these gases with alkanolamines, but the lack of reliable and accurate vapor-liquid equilibrium (VLE) data impedes the commercial application of more efficient alkanolamine systems. The objective of this research was to develop an FTIR apparatus and an in-situ technique capable of making VLE measurements of acid-gas-aqueous alkanolamine systems and to improve the accuracy of vapor-liquid equilibrium measurements at low hydrogen sulfide and carbon dioxide concentrations. The new FTIR apparatus and technique were tested in VLE measurements of low concentrations of carbon dioxide and hydrogen sulfide in aqueous mixtures of diethanolamine.
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  • 151
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    AIChE Journal 43 (1997), S. 2605-2608 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 152
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    AIChE Journal 43 (1997), S. 2911-2920 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The metering operation in the transfer-roll coating process is crucial for achieving a good uniformity and suitable thickness of the coating film. Experimental results carried out on a laboratory coater are reported. This coater mimics industrial flow conditions: it has a transfer roll and a metering-rod diameter similar to those found on a pilot coater, it operates at commercial speed, and the cover of the transfer roll is deformable. The experimental apparatus is described first. Then, a video analysis of the rib pattern is presented. Some interesting features are shown, in particular the existence of an inertia regime at high speed. The nip flow hydrodynamics are investigated using measurements of the pressure profile. It is shown that the film stability is strongly linked to the flow at the exit of the nip. The analysis of the maximum pressure in the nip, for various fluid viscosities and operating parameters, is represented using a master curve.
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  • 153
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    AIChE Journal 43 (1997), S. 2948-2959 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Transport models of diffusion-induced bubble growth and collapse in viscous liquids are developed and evaluated. A rigorous model for these important phenomena is formulated taking into account convective and diffusive mass transport, surface tension, and viscous and inertial effects. Predictions for bubble growth dynamics demonstrate the importance of viscous effects in the liquid surrounding the bubble for a wide range of conditions having relevance to polymer processing operations. It is also shown how previous models employing various approximations can be derived from the rigorous model by using different mathematical methods and dimensional analysis. Predicted bubble growth dynamics from the rigorous and approximate models are compared to establish the ranges of validity for two commonly used approximations. These comparisons indicate that models using a thin boundary-layer approximation have a rather limited range of applicability. A new approximate model, based on a previously published result, gives reasonably accurate bubble growth rate predictions with a significant reduction in computational effort.
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  • 154
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    AIChE Journal 43 (1997), S. 2997-3006 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Based on the absolute-rate theory, a consistent interpretation was provided for the dependence of surface-diffusion coefficient, Ds, on temperature and the amount adsorbed in various liquid-phase adsorption systems, such as the Langmuir-, Freundlich-and Jossens-type adsorption. It was demonstrated that a restricted molecular diffusion model for surface diffusion was useful for the analysis of the characteristic features of Ds. A formulation of Ds was derived based on the model and was applied to the analysis of surface-diffusion phenomena in various adsorption systems. The temperature dependence could be interpreted by assuming surface diffusion as an activated process. By taking into account the change in both the logarithmic slope of an adsorption isotherm and an adsorption potential, the concentration dependence of Ds could be interpreted irrespective of the type of the adsorption isotherms.
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  • 155
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    AIChE Journal 43 (1997), S. 3042-3058 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Polymer reactor control problems often lack frequent measurements of polymer properties, while other reactor environment measurements, such as temperatures, are readily available. The experimental application of a new estimator for handling such multirate measurement systems is presented. The estimator, in conjunction with a detailed nonlinear model and all measurements at their respective sampling rates, is able to provide frequent predictions of the process variables related to the quality (weight-average molecular weight) and quantity (monomer conversion) of the polymer product. The experimental application of a multivariable, nonlinear model-based predictive controller using reactor temperature and initiator flow rate as the manipulated variables for controlling weight-average molecular weight and monomer conversion is presented. The control strategy is designed to handle control nonaffine systems (nonlinear in the manipulated variables), while allowing for the incorporation of rate and amplitude constraints on the manipulated variables. A continuous methyl methacrylate solution polymerization pilot plant was used for the experiment.
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  • 156
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    AIChE Journal 43 (1997), S. 3095-3104 
    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 for a catalytic membrane reactor for oxidative coupling of methane (OCM), in which the membrane acts as an oxygen distributor to a bed of catalyst, is presented. From experimental data obtained using several silica membranes impregnated with Li and/or Na, which were prepared by the sol-gel method using alumina supports, the catalytic activity of the membrane was included in the so-called real membrane reactor (RMR) model. Then, the RMR performance was compared with that of the ideal membrane reactor (IMR), whose membrane was supposed to have no activity for the OCM and with experimental data obtained in membrane reactors. Since the membrane activity was implemented in the RMR model, for the first time in the literature, maxima in the hydrocarbon selectivity-methane conversion curves were predicted in agreement with previous experimental trends. Besides, the IMR performance was compared with that of the fixed-bed reactor (FBR), giving the maximum improvement of a membrane reactor over the FBR. Key factors for the future improvement of the performance in this kind of membrane reactor are deduced from these simulations.
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  • 157
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Active organic molecules are grafted on the xerogel silica matrix by using functionalized alkoxides f-R′-Si(OEt)3, where f is a chemical function and R′ is an alkyl spacer to limit the degrees of freedom of the molecules. Organic-inorganic hybrid films are prepared in which optically nonlinear DRl chromophores are covalently bound to the silica network. These films exhibit a large and stable second-order nonlinear coefficient from second harmonic generation experiments. Protoporphyrin molecules are attached double covalently to the xerogel matrix via flexible organic spacers. Persistent spectral holes are still burnt with moderate fluency at 120 K.
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  • 158
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    AIChE Journal 43 (1997), S. 2832-2836 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Partially polycondensed γ-aminopropylsilanetriol (APSTOL) was used as the silica precursor to prepare magnesium orthosilicate in the form of crystalline forsterite. Aqueous solutions of APSTOL and magnesium acetate were mixed and dried forming a water-soluble product that was converted into forsterite by heating to 1,000°C. The thermal evolution of the system was studied using TGA, FTIR, UV-VIS spectrophotometry, and XRD techniques, especially for the acetate decomposition and transformation of CSiO3-tetrahedra into the orthosilicate anions. The combustion of organics and the crystallization of forsterite proceed at temperatures 350 and 870°C, respectively. At intermediate temperatures, the system contains amorphous silicates with oligomeric and polymeric anions, which gradually depolymerize as temperature increases. The resulting crystalline product contains less impurities (periclase and enstatite) than samples prepared using other wet-chemistry techniques.
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  • 159
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: As a part of fundamental study on the kinetics of electroceramics processing by wet chemical methods, barium titanate precursor gel was prepared using barium acetate and titanium tetra-isopropapoxide as starting materials. Experimental results indicated that barium acetate was distributed uniformly in the gel matrix formed by hydrolysis and polymerization of titanium tetra-isopropoxide. In the subsequent calcination of the gel, rapid formation of barium titanate was observed above 823 K, which resulted from the reaction between titania and barium carbonate or barium oxide(s). The dynamics of barium titanate formation under different heat-up programs was successfully simulated based on a proposed reaction model that incorporates a specified reactive portion of barium acetate in the gel matrix.
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  • 160
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    AIChE Journal 43 (1997), S. 2857-2864 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Elemental depth profile examined using secondary-ion mass spectroscopy and structural profile examined using grazing-incident X-ray diffractometry were applied to analyze the growth behavior of Pb1-xLax(ZryTi1-y)O3 (PLZTO) and Pb1-xLaxTiO3 (PLTO) thin films deposited on a Si substrate. When deposited under a suitably high substrate temperature, the chamber's oxygen pressure was observed to substantially influence the structure of the films. Low oxygen pressures (PO2 〈 0.01 mbar) deteriorate crystal structure without altering the composition of the films. Deposition of a buffer layer enhanced the formation kinetics of PLZTO and PLTO films. However, sufficiently thick SrTiO3 (∼500 nm) layer was required to achieve this effect. Using (La0.5Sr0.5)CoO3/Pt materials as double-layer electrodes not only prevented the film-to-substrate interaction, but resulted in preferentially oriented thin films. Ferroelectric properties of the films were thus greatly improved, with remanent polarization (Pr) around 14 ∼ 16 μC/cm2, coercive force (Ec) around 50 ∼ 60 kV/cm, and relative dielectric constant (ε) around 900 ∼ 1,000.
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  • 161
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    AIChE Journal 43 (1997), S. 2650-2656 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A process for synthesis of ultrafine ceramic particles using a high-temperature flame is described. Thermodynamic calculations for the Si-C-O-H system were performed using a computer program for calculation of complex chemical equilibrium compositions. Possible synthesis of ultrafine SiC partcles using Si, SiO, and SiO2 powders (1.0-3.0 μm) as Si sources was investigated using an electric furnace (5 kW) at 2,018 K. Particle products were characterized mainly by X-ray diffraction analysis, field emission scanning electron microscopy, and thermogravimetry-differential thermal analysis. Ultrafine particles (18-29 nm) of cubic SiC (β-SiC) could be produced through Si + CH4, SiO + CH4 and SiO2 + CH4 reaction systems, respectively. The effect of hydrogen addition on the synthesis of SiC was also investigated. Ultrafine particles of 96.0% SiC selectivity were obtained when H2 was added to the SiO + CH4 reaction system, and the CH4/SiO molar ratio in this case was 2.0.
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  • 162
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    AIChE Journal 43 (1997), S. 2670-2678 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experimental investigations of high-temperature kinetics of Si-precursor molecules relevant to CVD and ceramic processing are described. Reaction systems using SiH4, Si2H6, and SiCl4 highly diluted in argon were studied in a shock tube, a high-temperature wave reactor, by monitoring in situ the concentrations of atomic or radical reactants Si, H, Cl, SiH, and SiH2. Because of the very high dilution, the measured properties are sensitive to a limited number of elementary reactions, allowing a relatively direct determination of the respective rate coefficients. Both thermal pyrolysis and laser flash photolysis methods were used to expand the investigated temperature range. An overview of the bimolecular Si-atom reactions is given.
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  • 163
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    AIChE Journal 43 (1997), S. 2741-2750 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The partial oxidation of methane to synthesis gas (syngas, CO + H2) was performed in a mixed-conducting perovskite dense membrane reactor at 850°C, in which oxygen was separated from air and simultaneously fed into the methane stream. Steady-state oxygen permeation rates for La1-xA′xFe0.8 Co0.2O3-δ perovskite membranes in nonreacting air/helium experiments were in the order of A′x = Ba0.8 〉 Ba0.6 〉 Ca0.6 〉 Sr0.6. Deep oxidation products were obtained from a La0.2 Ba0.8 Fe0.8 Co0.2 O3-δ disk-shaped membrane reactor without catalyst, with a 4.6% CH4 inlet stream. These products were further reformed to syngas when a downstream catalytic bed was added. Packing the 5% Ni/Al2O3 catalyst directly on the membrane reaction-side surface resulted in a slow fivefold increase in O2 permeation, and a fourfold increase in CH4 conversion. XRD, EDS, and SEM analyses revealed structure and composition changes on the membrane surfaces. Oxygen continuously transported from the air side appeared to stabilize the membrane interior, and the reactor was operated for up to 850 h.
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  • 164
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    AIChE Journal 43 (1997), S. 2751-2759 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dense intermetallic and ceramic (alumina based) coatings can be formed in situ during simultaneous combustion synthesis and densification in the field of centrifugal forces. Both microstructure and composition of alumina-based coatings formed during alumino-thermal reduction of oxides can be altered by an introduction of additives such as ZrSiO4, SiO2, Na2CrO4, and carbon. The activation energy and frequency factor for the Ni-Al reacting system consisting of equal atomic amounts of Ni and Al powders with an average particle size of 5 μm were measured using a nonisothermal technique, which were equal to 1.05 × 105 J/mol and 1.017 × 108 s-1, respectively. A mathematical model of in-situ densification of a single-phase combustion product (NiAl) in the field of centrifugal forces was developed and explored.
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  • 165
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    AIChE Journal 43 (1997), S. 2793-2801 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Hexagonally-packed mesoporous Nb-doped silica molecular sieves were hydrothermally synthesized with various siliceous sources and dopant concentration levels. The microstructure of mesoporous materials was characterized by a variety of physico-chemical methods. The pore packing order of the Nb-doped material depended strongly on the synthesis conditions such as aging temperature, pH of reaction mixture, surfactantto-Si ratio, and dopant concentration. Different silica precursors gave rise to different reactivity with the Nb dopants and interactions with the surfactants. The pore size and surface area of the materials can be systematically varied. The chemical environment of the Nb dopants in the silica framework was studied by XPS, EPR, PA-FTIR, UV-Vis, and 29Si MAS NMR. The results indicated that the Nb5+ ions were well dispersed in the framework of the mesoporous silica. The diffuse-reflectance UV-Vis spectrum of the mesoporous Nb-doped silica is red-shifted with respect to pure mesoporous silica. The 29Si MAS NMR spectrum contained a broad component at about -105 ppm, which may have been attributed to the presence of Nb-O-Si bonding in the mesostructure.
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  • 166
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    AIChE Journal 43 (1997), S. 2571-2578 
    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 two-phase swirl-flow monolithic-type reactor was designed to study the kinetics of heterogeneous photocatalytic processes on immobilized semiconductor catalysts. True kinetic rate constants for destruction of a textile dye were measured as a function of wavelength of light intensity and angle of incidence, catalyst layer thickness, and the effect of absorption of light by liquid film on the overall rate of photocatalytic degradation. Photocatalytic activities of two commercially available TiO2 catalysts (Degussa P25 and Hombikat UV 100) were also compared for different light intensities and catalyst layer thickness. Residence time distribution and mass-transfer limitations were evaluated. This new reactor appears to be an attractive choice for kinetic studies of heterogeneous photocatalysis.
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  • 167
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    AIChE Journal 43 (1997), S. 2601-2604 
    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 43 (1997), S. 3274-3274 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 169
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    AIChE Journal 43 (1997), S. 3264-3270 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 7 Ill.
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  • 170
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    AIChE Journal 43 (1997), S. 13-24 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In most industrial gas-phase polyethylene reactors, heat is removed by cooling the recycle gas stream in an external heat exchanger, where a portion of the vapor is condensed. The condensate evaporates in the reactor to absorb heat released by polymerization reactions, thereby increasing the production capacity of the unit. Nonequilibrium methods of multicomponent condensation are applied to develop a 1-D model to simulate the cooling unit of an industrial polyethylene reactor system operated in partial condensing mode. Finite difference approximations are used to convert the resulting set of differential equations to algebraic equations. A practical method of solving the equations is to combine the rapid local convergence of Newton's method with a globally convergent strategy. Correlation methods for estimating local heat-transfer coefficients in the liquid film layer are discussed. Butterworth's method for shear-stress-controlled condensate flow gives reasonable agreement between simulation results and industrial data, while Chen et al.'s method can better describe the transition process of condensate flow from laminar to turbulent flow.
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  • 171
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    AIChE Journal 43 (1997), S. 877-892 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two-dimensional time-dependent calculations for a molecular model of finite extensibility in the journal-bearing geometry are presented. The flow is considered to be incompressible and isothermal. The momentum conservation equation is integrated using a time-marching procedure in which local ensembles of dumbbells act as stress calculators. The calculations are based on the Calculation of non-Newtonian flows: finite elements and stochastic simulation technique (CONNFFESSIT) and combine deterministic (finite elements) and stochastic techniques to advance the velocity and stress fields in time. The ability of CONNFFESSIT to treat models for which no closed-form constitutive equation can be derived is illustrated by performing calculations using FENE dumbbells. Significant differences in the stress field between the true FENE and the linearized FENE-P are found, especially during the inception period. Steady-state kinematics are, however, identical within error bars for both FENE and FENE-P and for the Newtonian fluid. The essential algorithm of 2-D CONNFFESSIT is detailed, as well as experience gathered from its parallel and vector versions.
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  • 172
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    AIChE Journal 43 (1997), S. 902-912 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Simple first-order closure models for covariances of concentration fluctuations, for use in modeling turbulent flow reactors, were tested by direct numerical simulations. Concentration covariances and other statistical functions were evaluated for a series parallel reaction scheme in decaying, homogeneous turbulent flow. The simulations involve solving the unsteady Navier-Stokes and mass conservation equations by a pseudo-spectral method in a 643 wavenumber domain, with initially segregated reactants, for an initial turbulence Reynolds number of 29.9. Simulation results show that covariances of concentration fluctuations normalized with respect to mean concentration values are almost constant and that the time dependence of concentration covariances can be estimated if the mean concentrations are known at any one time after the initial time. Predictions of the first-order closure models of Bourne and Toor, Brodkey and Lewalle, Li and Toor, and Dutta and Tarbell were compared to simulation results. While none of these closures are satisfactory for all the conditions tested, the Brodkey-Lewalle closure agrees best with the simulations.
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  • 173
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In this work, on-line calorimetry was used to estimate the conversion and the copolymer composition in emulsion polymerization systems. Real-time feedback control of the polymer composition during the semibatch emulsion copolymerization of vinyl acetate and butyl acrylate was carried out. Both homogeneous copolymers and copolymers with previous defined composition profiles were obtained. It was shown that the feedback control was able to avoid monomer accumulation in the reactor, and hence potentially dangerous thermal runaways, without any deleterious effect on the polymer composition, when a sudden inhibition was caused by deliberately adding a solution of hydroquinone. The use of feedback control for the maximization of the production rate under safe conditions in the unseeded emulsion copolymerization of vinyl acetate and VeoVa10 (an alkyl vinyl ester from Shell) is also presented.
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  • 174
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    AIChE Journal 43 (1997) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 175
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    AIChE Journal 43 (1997), S. 1117-1121 
    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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  • 176
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    AIChE Journal 43 (1997), S. 1125-1140 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Expression of the time-averaged equations for the conservation of momentum and energy in terms of the fractions of the local shear stress and heat flux density, respectively, due to turbulence is shown to result in greatly simplified representations for fully developed flow and convection in round tubes and parallel-plate channels as compared to those in terms of the eddy viscosity, eddy conductivity, or mixing length. On the other hand, the turbulent Prandtl number is shown to be a fundamental characteristic of flow and convection rather than simply an artifact of the eddy diffusional model. The new simplified representations provide the basis for improved predictions of the velocity distribution, the friction factor, the temperature distribution, and the Nusselt number. The adaption of these new representations for other geometries and for developing convection is discussed briefly.
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  • 177
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    AIChE Journal 43 (1997), S. 1141-1152 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A dynamic model has been developed to predict the transient behavior of the temperature, the heat removal rate by the in-bed heat exchanger, and the flue-gas oxygen concentration for a circulating fluidized-bed (CFB) combustor. The model was incorporated into a control simulator to reproduce the combustion process within the overall program. The simulator predicts the behavior of the combustor under manual or automatic control to allow testing of control strategies. The model is validated by comparison with step-response tests carried out on a pilot CFB combustor. Discrepancies are attributable to unmodeled disturbances. Further validation, necessary to ensure the applicability of the simulator to control development, is provided by comparing control models identified experimentally using the pilot CFB to those obtained by simulation. Favorable comparison suggests that the dynamic model is suitable for use in control simulation.
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  • 178
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    AIChE Journal 43 (1997), S. 1163-1170 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The hydrodynamic characteristics of a new type of reactor, the immobilized soil bioreactor, were studied. This apparatus is a practical new engineering concept (soil immobilization) based on entrapment of soil particles, which contain pollutant-degrading microorganisms, in the pores of a geotextile to activate the indigenous microorganisms. The soil immobilization is the third on the size scale of immobilization processes, coming after (1) that of molecules in heterogeneous catalysis (in Angstrom) and (2) that of microbial cells and their fragments in immobilized cells and enzymes biocatalysis (in micron). The size of immobilized soil particles is in the range of a millimeter. A mathematical model of liquid flow within the reactor is proposed, which qualitatively explains the distribution of the immobilized soil in space. The dynamics of soil immobilization within the bioreactor has been studied as a function of the particle size, initial slurry concentraion and air flow rate. A mathematical model of the process of soil immobilization was proposed based on deep filter mechanics. The process can be described by a second-order kinetic model. This study will be of great importance for the design of immobilized soil bioreactors for degradation of recalcitrant soil pollutants.
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  • 179
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    AIChE Journal 43 (1997), S. 1250-1264 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A systematic method that quantitatively assesses property prediction uncertainty (imprecision) on optimal molecular design problems is introduced. Propety-structure relations are described with specific nonlinear functionalities based on group contribution methods. Property prediction uncertainty is explicitly quantified by using multivariate probability density distributions to model the likelihood of different realizations of the group contribution parameters. Assuming stability of these probability distributions, a novel approach is introduced for transforming the original nonlinear stochastic formulation into a deterministic MINLP problem with linear binary and convex continuour parts with separability. The resulting convex MINLP formulation is solved to global optimality for molecular design problems involving many uncertain group contribution parameters. Results indicate the computtional tractability of the method and the profound effect that property prediction uncertainty may have in optimal molecular design. Specifically, trade-off curves between performance objectives, probabilities of meeting the objectives, and chances of satisfying design specifications offer a concise and systematic way to guide optimal molecular design in the face of property prediction uncertainty.
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  • 180
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    AIChE Journal 43 (1997), S. 1287-1299 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The fugacity coefficients of the hydroperoxyl radical in supercritical water are estimated through molecular simulations. A potential function for the radical is first derived from ab initio self-consistent field molecular orbital calculations at the unrestricted Hartree-Fock level and from data in the literature. Molecular dynamics simulations of the hydroperoxyl radical are then performed in supercritical water and the fugacity coefficient of the radical is calculated by the free-energy perturbation method using the dynamic coupling parameter window-modification technique. The values of the fugacity coefficients at 773 K differ from unity. This methodology facilitates the incorporation of thermodynamic nonidealities in mechanism-based kinetic models for free-radical reactions in supercritical water.
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  • 181
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    AIChE Journal 43 (1997), S. 1813-1818 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The catalytic hydrogenation of alpha-methylstyrene to cumene is studied in a laboratory trickle-bed reactor operated at low liquid flow rates. Under this condition, wetting is not complete, vaporization of the liquid phase may occur, and reaction could proceed via liquid-solid and gas-solid catalysis, which increase the hydrogenation rate significantly. To determine and quantify the effect of the gas-solid catalyzed reaction, we propose the use of post-packing sections of increasing lengths. The inert bed acts as an absorber of the gas-phase-produced cumene. The liquid and gas effluent were monitored. Experimental global rates determined from liquid cumene concentrations varied with the post-packing length. A simple one-dimensional model developed shows that theoretical and experimental results agree well.
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  • 182
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    AIChE Journal 43 (1997), S. 1838-1848 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Opportunities exist to exploit the unique properties of carbon dioxide to process polymers for advanced applications. The diffusion of deuterated water in poly(methyl methacrylate) films swollen by carbon dioxide at 35°C over the pressure range 0 to 90 bar (corresponding density range: 0.0 to 0.66 g/cm3) was measured using in situ FTIR spectroscopy. The mechanism and time scale of the diffusion of deuterated water in PMMA are easily controlled by manipulation of the applied CO2 density. The enhancement of mass transport rate is consistent with the degree of plasticization of the polymer due to the absorption of carbon dioxide.
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  • 183
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    AIChE Journal 43 (1997), S. 1884-1893 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Clathrate phase equilibria for the ternary water-phenol-carbon dioxide system containing one-guest and two-host components were studied. Three four-phase equilibrium loci for this ternary system were determined over wide temperature and pressure ranges. A quintuple point, thermodynamically unique, and invariant condition appeared in this type of ternary system, was carefully measured, and were 293.7 K and 57.2 bar. At this quintuple point, five individual phases of water-rich liquid, phenol-rich liquid, carbon dioxide-rich liquid, phenol clathrate, and vapor could coexist in equilibrium. A new experimental technique was used to determine the liquid-phase compositions coexisting with phenol clathrates at the isobaric conditions of 30.0 bar and six temperatures ranging from 278.2 and 303.2 K. A potential applicability of the clathration process to phenol separation from aqueous solutions was demonsrated in terms of phenol concentrations based on carbon dioxide-free concentration. In particular, phenol separation by using high-pressure carbon dioxide as a clarthrate-inducing agent could be applied even to multiphase aqueous solutions over an entire range of phenol concentrations.
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    AIChE Journal 43 (1997), S. 1947-1954 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Recent experimental validation of theoretical and numerical predictions regarding scalar variance decay in a pipe have revealed that the traditional plug-flow reactor picture of pipe flow omits key physical mechanisms. In particular, the far-field decay exhibits a power law rather than exponential decay. These observations are examined by performing a set of experiments where the manner in which the scalar constituents are introduced into the pipe is varied. Significant differences are noted in the behavior of the variance decay until the very far field is reached, where an invariant power-law form emerges.
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    AIChE Journal 43 (1997), S. 1935-1946 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Explicit algebraic scalar-flux models that are valid for three-dimensional turbulent flows are derived from a hierarchy of second-order moment closures. The mathematical procedure is based on the Cayley-Hamilton theorem and is an extension of the scheme developed by Taulbee. Several closures for the pressure-scalar gradient correlations are considered and explicit algebraic relations are provided for the velocity-scalar correlations in both nonreacting and reacting flows. In the latter, the role of the Damköhler number is exhibited in isothermal turbulent flows with nonpremixed reactants. The relationship between these closures and traditional models based on the linear gradientdiffusion approximation is theoretically established. The results of model predictions are assessed by comparison with available laboratory data in turbulent jet flows.
    Additional Material: 7 Ill.
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  • 186
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    AIChE Journal 43 (1997), S. 1988-1988 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 187
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    AIChE Journal 43 (1997), S. 1964-1974 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The use of optical fibers in a fluorescence-detection scheme permits the accurate determination of the radial distribution of the transit time, the column efficiency, and the analyte concentration at the exit of a chromatographic axial-compression column (50 mmID). The results obtained demonstrate that the column is not homogeneous, but suggest a nearly cylindrical distribution of the packing density. The average velocity close to the column wall is 7% lower than along its axis and the HETP 25% higher. The lack of homogeneity of the column packing is another source of band broadening not taken into account in chromatography so far. It causes the apparent HETP derived from the conventional elution chromatogram recorded on the bulk eluent to be larger than the local HETP and the band profile to be unsymmetrical with a slight tail reminiscent of kinetic tailing.
    Additional Material: 9 Ill.
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  • 188
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    AIChE Journal 43 (1997), S. 1975-1988 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Hollow-fiber membrane processes with a constant external resistance having a constant or variable shell concentration resulting from an operational mode of cocurrent or countercurrent are studied. By solving numerically the continuity mass-conservation equation with the corresponding boundary conditions, the lumen laminar mass-transfer coefficients for both cases are correlated. The correlations greatly improve the calculating accuracy of the overall mass-transfer coefficient and can be used to obtain the lumen mixed-cup concentration by an algebraic equation substituting the partial differential equation. A separation factor m' is introduced to characterize the effect of the operational mode. Calculation results demonstrate that the lumen mass-transfer coefficient is independent of the real lumen and shell concentrations, but it is greatly influenced by m'. The countercurrent mode, compared to the cocurrent mode, provides not only a higher mean driving force, but a higher lumen mass-transfer coefficient. This conclusion is novel and valid for the tube-shell heat or mass-transfer processes and is supported by the experimental data in the literature and our gas membrane separation experiments.
    Additional Material: 9 Ill.
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  • 189
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    AIChE Journal 43 (1997), S. 1989-2001 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Sheet and film processes pose a challenging identification and control problem due to high complexity, poor conditioning, and limited input-output data. The interaction between model accuracy and closed-loop performance is explored for sheet and film processes using a model decomposition in terms of two static orthogonal matrices in series with a diagonal transfer-function matrix. It is shown that the accuracy of the diagonal elements of the transfer-function matrix directly specifies the closed-loop performance achievable by a model-based controller. This motivates the development of a combined identification and control procedure in which the controller is designed to be robust to model inaccuracies quantified during identification. The resulting controller is compared to an industrially accepted controller design method for two examples, including a simulated blown-film process. Based on the theoretical results and simulations, it was concluded that the poor performance often reported for existing industrial sheet and film process-control systems is likely due to signs of the model gains being incorrectly identified.
    Additional Material: 14 Ill.
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  • 190
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    AIChE Journal 43 (1997), S. 2021-2033 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The problem of simultaneous control of composition and molecular weight of copolymers produced in semicontinuous emulsion polymerization is addressed. A first-principles model of emulsion copolymerization is used to produce optimal open-loop policies, which are then experimentally tested on the system methyl methacrylate/vinyl acetate. In contrast to earlier work in the control of semicontinuous emulsion copolymerization, the control problem addressed has multiple inputs and multiple outputs, and the experimental application is free of empirical correlations and performed on an unseeded system. Optimal open-loop policies are calculated efficiently by optimizing properties of the instantaneous polymer being formed. The experimental results confirm the feasibility of these techniques. A model-predictive control scheme, in which optimal policies are recomputed on-line to account for disturbances, is proposed. The scheme, which exploits the advantages of the efficient calculation of optimal policies, is tested by simulation showing good performance.
    Additional Material: 12 Ill.
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  • 191
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    AIChE Journal 43 (1997), S. 2073-2082 
    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 one-dimensional nonequilibrium model for multicomponent condensation is used to simulate a vertical single-pass shell-and-tube heat exchanger in an industrial gas-phase polyethylene reactor system. Starting the calculation at the top of the exchanger, the model can predict temperatures at the bottom of the exchanger within an accuracy of ±5 K as compared to three sets of industrial data. Sensitivities of model predictions were analyzed, including uncertainties associated with physical and transport property estimates, step size, and convergence criterion. Model predictions are not particularly sensitive to the estimation errors of physical and transport properties if K values are calculated using an equation of state applicable to both liquid and vapor phases. Effects of operating conditions on heat removal from polyethylene reactors were investigated for an existing process. It was quantitatively demonstrated why and how severely noncondensable gases impede condensation heat transfer. The level of noncondensable gases and the cooling water temperature are the two most important factors influencing the heat-removal rate. Replacing a portion of noncondensable gas, such as N2, with a condensable fluid that is inert to polymerization reactions can substantially increase the heat-removal rate from the reactor, thereby allowing for an increase in polymer production rate.
    Additional Material: 5 Ill.
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  • 192
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    AIChE Journal 43 (1997), S. 2083-2095 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Ignitions, extinctions, and Hopf bifurcations in methane oxidation were studied as a function of pressure and inlet fuel composition. A continuous stirred-tank reactor was modeled with numerical bifurcation techniques, using the 177 reaction/31 species mechanism. Sensitivity and reaction pathway analyses were performed at turning points to identify the most important reactions and reactive species. Then, simulations were compared with experimental data. Multiple ignitions and extinctions as well as oscillations that are purely kinetically driven were found. Ignition to a partially ignited state with considerable reactivity of methane indicates possible narrow operation windows with high selectivities to partial oxidation products. At 0.1 atm, we found a selectivity of up to 80% to CO at 70% CH4 conversion. The ignition to a fully ignited branch is associated with high selectivity to CO2 and H2O. The C2 chemistry inhibits the ignition of methane to the partially ignited branch. The methane ignition temperature exhibits two branches with respect to pressure, with only the low-pressure branch being dominant. Reaction path analysis at ignition conditions shows that the preferred pathway of CH4 oxidation is to form CO and CO2 through CH2O and CH2(s) intermediates. However, at intermediate to high pressures, the recombination of CH3 to C2 H6 also becomes quite significant.
    Additional Material: 14 Ill.
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  • 193
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    AIChE Journal 43 (1997), S. 2096-2111 
    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 approach to the use of pulsed-gradient spin echo (PGSE) NMR methods for the measurement of flow and diffusion in porous media is presented, in which the fluid dynamics is probed over well-defined temporal and spatial domains. Various NMR techniques based on PGSE encoding are described in the context of standard theories of dispersion, with reference to Eulerian and Lagrangian coordinate frames. This array of methods provides access not only to the dispersion coefficient and the mean local velocity but also to propagators relevant to spatial and temporal correlations. Methods investigated include flow imaging, average propagator analysis, dispersion measurement, velocity exchange spectroscopy, and flow and disffraction based on scattering analysis. We apply these to a study of flow and dispersion of water in a packed bed of 90.7-μm-dia. polystyrene latex spheres. Our measurements of the dependence on Peclet number of dispersion (parallel and perpendicular to the mean flow direction) are in excellent agreement with results reported in the literature. The scattering approach used here has potential for studying complex flow properties involving the interplay between hydrodynamic and structural characteristics of porous media.
    Additional Material: 13 Ill.
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  • 194
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    AIChE Journal 43 (1997), S. 2133-2136 
    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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  • 195
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    AIChE Journal 43 (1997), S. 2137-2140 
    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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  • 196
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    AIChE Journal 43 (1997), S. 2112-2122 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The transport of moisture in shrinking food gels during drying is studied based on a novel thermomechanical theory accounting for a structural transition in the material - from the rubbery to the galssy state - during drying. The proposed theory is applied to the drying of a model cylindrical starch-gluten gel system. The predicted drying characteristics depend on the Deborah number, a ratio of the characteristic relaxation time to the characteristic diffusion time. At low Deborah numbers, drying is Fickian. At intermediate and high Deborah numbers, however, drying is non-Fickian, leading to an apparent mass-transfer shutdown, which is a result of surface dryout and skin/shell formation. Based on a time-dependent surface boundary condition, the model proposes that surface drying is not only a function of the Biot number but also a function of the “Shell” number, a ratio of the Deborah and Biot numbers. The model is verified by comparing its predictions with experimental data from drying of starch-gluten gels at 22.5 and 40°C. The model predictions agree with experimental data and capture the observed sigmoidal shape of the experimental drying curves in the saturated flow regime. The predicted moisture profiles show shell formation and growth during drying, compatible with the experimental moisture profiles from the literature.
    Additional Material: 13 Ill.
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  • 197
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    AIChE Journal 43 (1997), S. 2261-2278 
    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 for assessing nonlinear interaction effects and closed-loop nonlinearity in multivariable processes is presented. It is based on a differential geometric interpretation of the relative gain array that leads naturally to systematic procedures for describing interaction effects of higher order and for assessing closed-loop nonlinearity effects in nonlinear processes. Two types of nonlinear effects associated with the behavior of a process are introduced. Between-channel nonlinearity is associated with the nonlinear dependence of an output channel on other input - output pairings. Withinchannel nonlinearity is used to identify the nonlinear effects that result from the inherent nonlinearity of an individual output channel. A root-mean-squared measure of nonlinearity is introduced and is used to evaluate the significance of local nonlinear effects. Nonlinear interaction measures are derived that provide tools for assessing input - output pairings in a nonlinear process. This new approach extends the standard techniques and provides an estimate of the effect of nonlinearity on closed-loop interactions.
    Additional Material: 4 Ill.
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  • 198
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    AIChE Journal 43 (1997), S. 2579-2595 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A comparison between experimental and theoretical results for the combined microwave and convective drying of softwood is presented. The microwave applicator used for the experiments was an oversized waveguide, and the results for both sapwood and heartwood were analyzed. To elucidate on the physics of the process at a fundamental level, a complete model is proposed, which considers the intricate link that transpires between the heat-and mass-transfer phenomena and the power distribution throughout the sample during drying. The resulting model, which uses a comprehensive 2-D set of equations to describe the drying process, together with a complete 3-D solution of the Maxwell equations within the waveguide in the time domain, can be used to investigate many aspects of dielectric drying. This research deals with the spatial variation of the power density within the material at various drying times and the effect of the anisotropy of the transfer properties on the shape and evolution of the power distribution. Most importantly, it focuses on the prediction of the location of hot spots and thermal runaway within the sample from the viewpoint of product quality. Strengths and weaknesses of the model are highlighted.
    Additional Material: 15 Ill.
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  • 199
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    AIChE Journal 43 (1997), S. 3147-3160 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The modeling of pressure filtration of flocculated suspensions using compressional rheology and a knowledge of compressional yield stress Py(φ) and a hydraulic resistance factor r(φ)(φ is the local volume fraction of solids) is shown to yield an initial solids loading that maximizes the throughput of the filter. The optimal initial height h0 is such that the filtration time to reach a specified average volume fraction as output equals the handling time for the filter press. The maximum throughput of the press is then examined as a function of the remaining control parameters, the initial solids volume fraction φ0, and the applied piston pressure δP. The dependence of filtration time on φ0/∞00 (where φ∞is the volume fraction of solids at infinite time under applied pressure δP) enables the construction of a simple numerical model for the pressure filtration process, which accurately approximates predictions of the full compressional rheology model.
    Additional Material: 15 Ill.
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  • 200
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    AIChE Journal 43 (1997), S. 104-117 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Computational fluid dynamics methods are used to provide three-dimensional simulations of a low-density polyethylene (LDPE) autoclave reactor under normal operating conditions. For the conditions used, the reactor is not very well mixed; thus, the common model approximation of a perfectly stirred reactor is not warranted. The simulations verify the sensitive nature of the polymerization reactors and indicate a need for optimizing operating parameters.
    Additional Material: 21 Ill.
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