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  • Chemical Engineering  (1,635)
  • 1995-1999  (1,635)
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 185-189 
    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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  • 2
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 190-194 
    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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  • 3
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 58-67 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Theoretical models of gas diffusion and permeation in microporous molecularsieve membranes are presented. The effect of the adsorbed diffusant on the total transmembrane flow is insignificant for permanent gases. For highly adsorbable gases the effect of the adsorbed molecules on the total transmembrane flux may be high at low temperatures. The activation energy of diffusion increases when the kinetic diameter of the diffusant increases. The activation energy of gas diffusion compares well with the values calculated based on the Lennard-Jones potential. Maximum possible permeability coefficients calculated for He in the molecular-sieve membranes do not exceed ˜30,000 Barrer at room temperature. The experimentally observed value for He permeability is ˜1,000 Barrer (T=30°C) because of the high tortuosity (τ≍ 25) and low porosity (θ = 0.22) of the membrane porous structure.
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  • 4
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 68-77 
    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 pH-stat MSMPR crystallizer is used to obtain the nucleation rate equation of calcite formed in the Na2CO3-CaCl2 reacting system. The experiments are conducted for seeded and unseeded runs. Effects of breakage and agglomeration on the crystalsize distribution are demonstrated. In a continuous operation, the agglomeration of nuclei followed by the breakage of agglomerates occurs at the transient state, while the agglomeration is significant at the steady state. Taking crystal agglomeration into account, the corrected nucleation rate and agglomeration rate are obtained simultaneously. The agglomeration rate is a function of relative supersaturation and magma density, and the corrected nucleation rate is approximately two- to five-fold of the apparent nucleation rate, which is the nucleation rate without considering the agglomeration effect. Discussed also is the formation of calcium carbonate polymorphism.
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  • 5
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 135-147 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Research on exothermic reactor operation has been based mostly on the classic two-state continuous stirred tank reactor model, implicitly assuming that the cooling jacket temperature dynamics are negligible. In this case, the cooling jacket temperature is the manipulated input instead of the cooling jacket flow rate for feedback control of reactor temperature. Adding a cooling jacket energy balance results in much more complex behavior than a simple lag effect. A stabilizing inner-loop cascade controller is assumed in the two-state CSTR model, because the three-state model incorporating cooling jacket temperature dynamics may be open-loop unstable when the two-state model is open-loop stable. The influence of design parameters on the multiplicity behavior of a three-state model is considered. Elementary catastrophe theory is used to study the effect of process parameters such as the cooling jacket flow rate, heat-transfer coefficient, heat of reaction, and cooling jacket feed temperature on the steady-state multiplicity of the three-state model. This multiplicity analysis is particularly relevant for control because the primary bifurcation parameter is the cooling jacket flow rate, the manipulated input for feedback control in the three-state model. This multiplicity analysis guides improvements in process design and/or operation to eliminate difficult operating regions associated with steady-state multiplicities; the presence of multiple steady states results in safety and operation problems due to ignition/extinction phenomena. Reactor scale-up affects the presence of these infeasible reactor operating regions. Certain design parameter changes that remove multiplicities in the two-state model cannot remove multiplicities in the three-state model.
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  • 6
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 346-356 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Brownian and molecular dynamics simulations are used to study rapid bimolecular reactions at near-infinite dilution in near-critical and supercritical fluids. We probe the dynamics of both nonreactive and reactive collisions and measure rate constants for reaction and collision. Collision rate constants are nearly independent of bulk solvent density, but affected by local solute-solute density enhancements at a given density: their magnitudes depend on the length scale for molecular encounters (cybotactic radius) in the reaction through the equilibrium solute-solute radial distribution function. In contrast, reaction rate constants asymptotically approach the gas-kinetic limit at low densities and the Smoluchowski liquid-like limit at high densities. They also display the same radial dependence as collision rate constants at lower densities and a direct dependence on the cybotactic radius at higher densities (as in the Smoluchowski theory). Their behavior is explained in terms of a transition from a collision-limited regime at low densities to a diffusion-limited regime at higher densities. The transition between these regimes depends on the cybotactic radius and the density of the system, the interplay of which causes shifts in the transition region which depend not only on the properties of the near-critical solvent: they differ for different reactions, even at the same solvent density. This explains some of the apparent inconsistencies among previous experimental and computational studies of reactions in supercritical fluid media.
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  • 7
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 402-414 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Many motile bacteria exhibit chemotaxis, the ability to bias their random motion to ward or away from increasing concentrations of chemical substances which benefit or inhibit their survival, respectively. Since bacteria encounter numerous chemical concentration gradients simulatneously in natural surroundings, it is necessary to know quantitatively how a bacterial population responds in the presence of more than one chemical stimulus to develop predictive mathematical models describing bacterial migration in natural systems. This work evaluates three hypothetical models describing the integration of chemical signals from multiple stimuli: high sensitivity, maximum signal, and simple additivity. An expression for the tumbling probability for individual stimuli (Brown and Berg, 1974) is modified according to the proposed models and incorporated into the cell balance equation for a 1-D attractant gradient (Ford and Cummings, 1992). Random motility and chemotactic sensitivity coefficients, required input parameters for the model, are measured for single stimulus responses. Theoretical predictions with the three signal integration models are compared to the net chemotactic response of Escherichia coli to co- and antidirectional gradients of D-fucose and α-methylaspartate in the stopped-flow diffusion chamber assay. Results eliminate the high-sensitivity model and favor the simple additivity over the maximum signal. None of the simple models, however, accurately predict the observed behavior, suggesting a more complex model with more steps in the signal processing mechanism is required to predict responses to multiple stimuli.
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  • 8
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 426-429 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 9
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 439-443 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 10
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 446-455 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Studies of heat and mass transfer in packed beds, which disagree substantially in their findings, have nearly all been done with beds of regular particles of uniform size, whereas oil-shale retorting involves particles of diverse irregular shapes and sizes. We, in 349 runs, measured mass-transfer rates from naphthalene particles buried in packed beds by passing through air at room temperature. An exact analogy between convection of heat and mass makes it possible to infer heat-transfer coefficients from measured mass-trans-fer coefficients and fluid properties. Some beds consisted of spheres, naphthalene and inert, of the same, contrasting or distributed sizes. In some runs, naphthalene spheres were buried in beds of crushed shale, some in narrow screen ranges and others with a wide size range. In others, naphthalene lozenges of different shapes were buried in beds of crushed shale in various bed axis orientations. This technique permits calculation of the mass-transfer coefficient for each active particle in the bed rather than, as in most past studies, for the bed as a whole.The data are analyzed by the traditional correlation of Colburn jD vs. Reynolds number and by multiple regression of the mass-transfer coefficient on air rate, sizes of active and inert particles, void fraction, and temperature. Principal findings are: local Reynolds number should be based on the active-particle size, not the average for the whole bed; differences between shallow and deep beds are not appreciable; mass transfer is 26% faster for spheres and lozenges buried in shale than in all-sphere beds; orientation of lozenges in shale beds has little or no effect on mass-transfer rate; and for mass or heat transfer in shale beds, log(j·∊) = - 0.0747 - 0.6344logNRe + 0.0592log2 NRe.
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  • 11
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 456-468 
    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 thermodynamics and transport properties of Lennard-Jones particles in pillared catalytic clays are studied by molecular dynamics simulation. The clays are represented by parallel sheets separated by a given distance and connected by pillars of a given size. Two different spatial distributions of the pillars are studied to determine their effect on the properties of the system. Calculations did not indicate a strong dependence of the diffusivity on the spatial distribution of the pillars, except at low porosities. The solvation force increases monotonically with decreasing porosity of the clays and increasing density of the molecules. The percolation threshold ϕc of the system is estimated from the diffusivity measurements in the limit of infinitely low sorbate densities. Near ϕc the diffusivity D vanishes according to the power law, D ˜ (ϕ - ϕc)n, where ϕ is the porosity of the system, and n is a universal constant. The simulations yield n ⋍ 1.7. Since 2- percolation systems require n ⋍ 1.3 and 3-D systems n ⋍ 2.0, pillared clays behave as a system with an effective dimensionality between 2 and 3.
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  • 12
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 337-345 
    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 monolith froth reactor, involving two-phase flow and a monolith catalyst, is developed. The flow within monolith channels, consisting of trains of gas bubbles and liquid slugs, is produced by forming a two-phase froth in a chamber immediately below the bottom of the monolith. The froth then flows upward into the monolith channels through pressure forces, which differs from previous methods since it may be carried out for a commercial-scale reactor. Because the liquid film which develops between the gas phase and the surface of the catalyst is extremely thin, two-phase flow within a monolith can provide reaction rates which are near their intrinsic values. Catalytic oxidation of aqueous phenol over copper oxide supported on γ-Al2O3 is used as a model reaction for investigating reactor performance. Generation of a froth is confirmed by visual inspection; the average bubble size is approximately that predicted by a force balance. The effect of externally controllable process variables (liquid and gas flow rates, temperature, and pressure) on the rate of phenol oxidation was investigated. Reaction rate increases with temperature or pressure increase and decreases with gas flow rate increase, achieving a maximum with respect to liquid flow rate. The activation energy calculated from the apparent reaction rate measured in the monolith froth reactor is similar to that of intrinsic value, suggesting minimal mass-transfer limitations.
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  • 13
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 377-388 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A thermogravimetric analyzer is used to study the synthesis of TiN from Ti powder over a wide range of temperature, conversion and heating rate, and for two Ti precursor powders with different morphologies. Conversions to TiN up to 99% are obtained with negligible oxygen contamination. Nonisothermal initial rate and isothermal data are used in a nonlinear least-squares minimization to determine the most appropriate rate law. The logarithmic rate law offers an excellent agreement between the experimental and calculated conversions to TiN and can predict afterburning, which is an important experimentally observed phenomenon. Due to the form of the logarithmic rate law, the observed activation energy is a function of effective particle size, extent of conversion, and temperature even when the intrinsic activation energy remains constant. This aspect explains discrepancies among activation energies obtained in previous studies. The frequently used sedimentation particle size is a poor measure of the powder reactivity. The BET surface area indicates the powder reactivity much better.
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  • 14
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 430-434 
    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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  • 15
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 435-438 
    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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  • 16
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    AIChE Journal 41 (1995), S. 501-508 
    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 primary method of reducing membrane fouling during cross-flow microfiltration is periodic reverse filtration. This in situ method of cleaning the membrane forces clear fluid in the reverse direction through the membrane and readjusts the particle or solute accumulation on the retentate side of the membrane. This work focuses on the design of a high-frequency, reverse-filtration strategy to maximize the flux for washed yeast suspensions through 0.2- μm cellulose acetate flat sheet membranes. Several experiments were conducted with reverse-filtration times ranging from 0.5-4 s and forward-filtration times ranging from 1-40 s. For every back-filtration time, there exists an optimum forward-filtration time that gives the maximum global average flux. The optimum average flux increases with decreasing back filtration times and feed concentrations, but shows little dependence on cross-flow velocity and reverse filtration transmembrane pressure. The optimum flux with rapid backflushing is 20 to 30 times higher than the long-term flux in the absence of backflushing. A theory presented assumes that cake formation during forward filtration follows dead-end filtration theory and the cake is instantly removed during reverse filtration. The measured average flux per cycle follows the trends predicted by the theory, but the measured values exceed the predictions, presumably due to brief delays in cake removal and cake formation at the start of reverse and forward filtration, respectively, during each cycle.
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  • 17
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 868-879 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Fluidized-bed polyethylene reactors are prone to unstable behavior and temperature oscillations (Choi and Ray, 1985b). Their work is extended to show the effects of ethylene feed system operation, reactor cooling system design, catalyst properties, and gas composition on reactor stability and dynamics. The analysis is performed using a well-mixed model, because heat- and mass-transfer resistances between multiple phases are small and are not required to account for the observed bifurcation phenomena. The addition of a gas recycle and heat exchanger system to the model significantly affects dynamic performance, including the formation of limit cycles. The size and dynamics of the heat exchanger, however, have little effect on the overall stability. In contrast, automation of the ethylene feed system to replace the monomer in the reactor as it is consumed leads to substantially different dynamic behavior than if the ethylene feed is maintained at a constant rate. Catalyst properties (multiple sites, activation energy, and deactivation) significantly affect dynamics and stability, whereas comonomer and other gases affect them only mildly. The results confirm that without proper temperature control, gas-phase polyethylene reactors are prone to instability, limit cycles, and excursions towards unacceptable high-temperature steady states.
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  • 18
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 924-927 
    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 Maxwell equal area rule is a basic construct for determining saturated phase volumes from equations of state. The fundamental idea is that for a pure substance a horizontal line drawn through the trace of an isotherm, which equalizes the van der Waals loops area above and below the line, intersects the isotherm at the saturated volumes.Another basic construct exists for determining the phase compositions in a binary mixture by establishing the tangent line to the total Gibbs energy curve plotted against composition. We demonstrate that finding the tangent also reduces to an equal area construction for the derivative of the total Gibbs energy plotted against composition. An efficient algorithm suggested effects such equal area determinations. The trial-and-error procedure normally converges in one to three steps to the correct solution given any resonable starting guess. Implementation using modern calculators with graphics capabilities is simple and straightforward.
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  • 19
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    AIChE Journal 41 (1995), S. 959-973 
    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 interaction between a winter flounder antifreeze polypeptide and an ice/water interface was studied using Molecular Dynamics computer simulation techniques to study the mechanism of action of this class of antifreeze molecules. Simple Point Charge models were used for the water molecules, and a molecular mechanics program (CHARMM) was used to construct the model for the polypeptide. A (2021) face was exposed on the ice surface, as this is believed to be the experimentally favored ice face for peptide binding. The polypeptide binds strongly to the ice surface even though it was placed with its four polar threonine (Thr) groups pointing away from the ice surface. This tested the previously advanced hypothesis that adsorption occurs primarily between these groups and the ice due to a matching of the spacing between oxygen atoms in the ice lattice and the polar Thr residues. As well as contacts with other polar groups on the peptide, the binding to the ice produces a good steric fit of the peptide with the corrugated ice interface. The presence of the peptide did not induce any melting of the ice at 200 K.
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  • 20
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    AIChE Journal 41 (1995), S. 985-990 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Computer simulation studies of refolding pathways and the formation of intermediates for a simple, 2-D lattice protein model are presented. The sequence of the 20-bead model protein chain is chosen so that hydrophobic beads will reside in the protein interior in the native state. Nonbonded hydrophobic beads attract each other with strength ∊ decreasing the |∊/kT| mimics increasing the concentration of the denaturant. Dynamic Monte Carlo simulations and exhaustive conformational searches have been performed on an isolated model protein sequence at different levels of |∊| (different denaturant concentrations). As the denaturant is withdrawn, the model protein exhibits a transition from a random coil state to a compact native state with a hydrophobic core. The refolding process is observed to be cooperative in that the chain does not start folding until the middle section has folded correctly, and proceeds along preferred pathways that are populated by distinct, partially folded intermediates.
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    AIChE Journal 41 (1995), S. 974-984 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A theoretical model for investigating physical phenomena underlying immune complex formation was developed, based on the statistical mechanical theory of associating fluids that identifies each molecule as a hard sphere with a nested point charge and vector dipole. The interaction between binding molecules (epitope-paratope binding) is represented as a cone truncated by two concentric spheres in which the potential energy is a modified square well with respect to particle separation and a square well with respect to mutual molecular orientation. Equilibrium binding results predicted by the model show good agreement with results obtained experimentally for a model system containing a single antigen and a single monoclonal antibody [bovine serum albumin (BSA) - anti-BSA antibody]. Moreover, values obtained for the system isothermal compressibility and the second virial coefficient by both the model and light scattering experiments also show good agreement with one another.
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  • 22
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    AIChE Journal 41 (1995), S. 855-867 
    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 a triplet competitive-consecutive halogenation sequence forming mono-, di- and trihalogenated products of the form, A + B → R + B → S + B → T, under semibatch operation adding B to A, if perfect mixing could be assumed at all scales, the product distribution would be unchanged on scaling up. However, if the reaction rates are reasonably faster than the mixing rate, the semibatch addition of B to A will be imperfectly backmixed, exhibiting macroscale concentration gradients. This partial segregation of the primary reagents is capable of modifying the selectivity and corresponding appearance of R, S and T in the course of the batch. Imperfect mixing is quantified using the networks-of-zones model. The effect of scaling up at equal tip speed is examined for a lab-scale 0.3-dm3 reactor, a semitech 30-dm3 reactor, and a production-scale 3,000-dm3 vessel. The intensity of partial segregation is weak at the lab scale, but very severe at the production scale. The lab-scale reactor is therefore close to perfectly backmixed, and the primary, secondary and tertiary products appear in sequence. At the semitech scale the increased partial segregation causes the final product to initially precede the secondary product paradoxically but lag the initial product. At the large scale the more severe segregation between A and B gives an even greater paradox, whereby the final product appears ahead of both the primary and secondary ones. The segregated concentration fields of A and B are visualized as sectional image reconstructions for networks comprising on the order of 1,000 zones. Localized intensive plumes of B emanating from the addition point cause the paradoxical reversals of product sequences. The calculations are directly relevant to real industrial miscible liquid halogenations for which product distribution paradoxes have been observed (Haywood, 1990).
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    AIChE Journal 41 (1995), S. 907-914 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Microporous solids made by polymerizing the organic phase of bicontinuous microemulsions stabilized with didodecyldimethylammonium bromide show surface areas as high as 70 m2/g. Small-angle X-ray scattering measurements on microporous copolymers containing polymethylmethacrylate show that these areas result from structures larger than 250 Å that are generated during polymerization. These X-rays measurements also show that the 17-Å structures characteristics of the original microemulsion are retained during polymerization, but destroyed when the detergent is extracted and the solid is dried.
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    AIChE Journal 41 (1995), S. 938-947 
    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-based on evaporation of a constant-composition droplet containing two components that differ markedly in volatility accurately estimates activity coefficients of both components. This new technique is developed to simultaneously determine the evaporation rate and composition of a droplet from intensity peaks observed in the light scattered by the droplet. It has no upper or lower limits on the relative volatility of the system and is particularly suitable for systems containing one relatively nonvolatile component. The data on the glycerol-ethanol system, obtained from evaporation of glycerol droplets in ethanol vapor and correlated with Margules and Wilson equations, are thermodynamically consistent. The results of this study agree with ethanol activity coefficients calculated from the total pressure vs. solution composition data previously reported.
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    AIChE Journal 41 (1995), S. 1184-1193 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mobile-phase additives, commonly used to modulate absorbate retention in gradient elution chromatography, are usually assumed to be either linearly retained or unretained. Previous theoretical work from our laboratory has shown that these modulators, such as salts in ion-exchange and hydrophobic interaction chromatography and organic modifiers in reversed-phase chromatography, can absorb nonlinearly, giving rise to gradient deformation. Consequently, adsorbate peaks that elute in the vicinity of the head of the deformed gradient may exhibit unusual shapes, form shoulders, and/or be concentrated. These effects for a reversed-phase sorbent with aqueous acetonitrile (ACN) as the modulator are verified experimentally. Gradient deformation is demonstrated experimentally and agrees with simulations based on ACN isotherm parameters that are independently determined from batch equilibrium studies using the layer model. Unusual adsorbate peak shapes were found experimentally for single-component injections of phenylalanine, similar to those calculated by the simulations. A binary mixture of tryptophan and phenylalanine is used to demonstrate simultaneous concentration and separation, again in agreement with simulations. The possibility of gradient deformation in ion-exchange and hydrophobic interaction chromatography is discussed.
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    AIChE Journal 41 (1995), S. 1550-1562 
    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 for treating three-dimensional current and temperature distributions in large-scale battety modules is described. Simulations are presented for a module consisting of cells formed with a lithium metal anode, a polymer electrolyte, and a vanadium oxide cathode. The calculations illustrate the nonlinear dependence of power output on system temperature, which for the investigated lithium-polymer battery module is determined primarily by the influence of temperature on the electrochemical reaction rates and ionic conductivity. An appendix is devoted to the estimation of physicochemical parameters, some of which are not available from the current literature, but are nonetheless important model inputs.
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    AIChE Journal 41 (1995), S. 1581-1584 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 41 (1995), S. 1602-1604 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 41 (1995), S. 1629-1639 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A fundamental study of drop collision, coalescence and growth induced by combined effects of gravitational and electrostatic forces is presented. The focus is on the enhancement of rates of collision and growth of spherical, conducting drops bearing zero net charge in dilute, homogeneous dispersions by an external electric field. By completely accounting for hydrodynamic and electrostatic interactions, a trajectory analysis is used to follow the relative motion of two drops equation is then solved to predict the evolution in time of the size distribution and the average size of drops. The results show that the rates of drop collision and growth can be increased significantly by applying an electric field, in accord with fundamental experiments and patents on electrocoalescence. The enhancement of drop collision and coalescence is especially pronounced when the imposed electric field acts horizontally, that is, in a direction perpendicular to gravity.
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    AIChE Journal 41 (1995), S. 1324-1328 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 41 (1995), S. 1341-1345 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 41 (1995), S. 1354-1355 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 41 (1995), S. 1389-1394 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The separation of air by pressure swing adsorption is improved by filling the interparticle voids in kineticaly selective adsorbent beds with fine particles of the adsorbent or inert material. He ratio of the average diameter of the coarse adsorbent particles to the average diameter of the fine particles, the size of the fine particles themselves, and the percent of volume of the fine particles in the bed are all critical to optimum PA performance.
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    AIChE Journal 41 (1995), S. 301-316 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Possibilities of predicting liquid holdup in rotating packed beds are examined using the film flow theory. A hydrodynamic model based on film flow on the particle scale accommodates both laminar and turbulent films in the entry and developed regime. Conductance measurement was used for experimental determination of liquid holdup and estimation of the degree of anisotropy of liquid distribution. Experimental results represent the first data for liquid holdup in the rotating packed bed as a function of operating conditions and liquid properties. They indicate an anisotropic liquid distribution dependent on the operating variables. While the film model can be fitted to the experimental data, such a fit lacks a theoretical basis and the classical theory of film flow on the particle scale cannot explain the liquid flow in rotating packed beds. An empirical expression correlates well the holdup data with the operating parameters.
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    AIChE Journal 41 (1995), S. 1926-1943 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Morphological aspects of the evolution of a gas - solid interface during typical CVD processes are presented, as well as a continuum model of CVD growth. A linear stability analysis used determines the effect of reactor conditions on the stability of planar growth. The main focus, however, is numerical solution of governing equations under a wide variety of conditions and with different initial interface shapes as starting point. Simplified solutions under specific deposition conditions and the numerical procedure for solving the complete system of equations are presented. The focuses are on the use of a parametrization that eliminates numerical problems encountered with steep interface gradients and the automatic generation of an adaptive mesh for the domain above the interface. Several examples illustrate the numerical solution procedure. To our knowledge, this is the first attempt to simulate interface evolution during CVD for long deposition times from various initial interface shapes. The simulation revealed several morphological phenomena observed experimentally in previous studies, including the formation of occlusions that contributes to film porosity and was clearly shown by the numerical results. Film uniformity strongly depends on the controlling mechanism of deposition. Severe nonuniformities develop under diffusional limitations, while deposition is very uniform under conditions of kinetics control. Film uniformity could be improved by choosing conditions for which a Damköhler number of deposition, Da, would have the lowest value.
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    AIChE Journal 41 (1995), S. 1723-1778 
    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 fluids posses properties that make them attractive as media for chemical reactions. Conducting chemical reactions at supercritical conditions affords opportunities to manipulate the reaction environment (solvent properties) by manipulating pressure, to enhance the solubilities of reactants and products, to eliminate interphase transport limitations on reaction rates, and to integrate reaction and separation unit operations. Supercritical conditions may be advantageous for reactions involved in fuels processing, biomass conversion, biocatalysis, homogeneous and heterogeneous catalysis, environmental control, polymerization, materials synthesis, and chemical synthesis. Moreover, supercritical fluids can be used profitably in fundamental chemical investigations of intermolecular interactions and their influence on chemical processes. Work on chemical reactions in and with supercritical fluids is reviewed. We discuss both fundamental studies and applications of reactions at supercritical conditions, with focus on work published after 1985.
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    AIChE Journal 41 (1995), S. 509-517 
    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 adsorbents for olefin/paraffin separation are synthesized by effective dispersion of Ag(I) and Cu(I) cations on substrates with hydrocarbon-phobic surfaces. These cations bind olefin molecules by a π-complexation bond, a weak chemical bond. Ethane/ethylene and propane/propylene separations are considered. Cation exchange resins and CuCl/γ-Al2O3 are effective substrates. On the Ag(I) resin at 25°C and 1 atm, the equilibrium adsorption ratio for C2H4/C2H6 = 9.2 and C2H4 capacity = 1.15 mmol/g; the corresponding values for C3H6/C3H8 = 10.4 and C3H6 capacity = 1.29 mmol/g. The CuCl/γ-Al2O3 sorbent shows equally promising results. The sorption rates are pore-diffusion-controlled and rapid. The olefin selectivity; capacity, and rates are much higher than all previous attempts and are suitable for applications in cyclic adsorption processes.The equilibrium data are correlated with an isotherm equation that accounts for both physical adsorption and π-complexation with energy heterogeneity, using only two true fitting parameters. Molecular orbital calculations using a C6H5SO3- substrate indicate that the π-complexation bond is contributed mainly by the donation of olefin π-bond electrons to the empty s-orbital of the metal, while the d-π* back donation contributes only 16%. Moreover, the relative order of the heats of adsorption is correctly predicted.
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    AIChE Journal 41 (1995) 
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    AIChE Journal 41 (1995), S. 1852-1863 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A nonequilibrium model for the dynamic simulation of distillation columns is described. The nonequilibrium model includes the direct calculation of the rates of mass and energy transfer and is better able to model the actual physical processes occurring on a real distillation tray than is the conventional equilibrium stage model. Example calculations show that heat-transfer limitations and the vapor holdup above the froth cannot be neglected at elevated pressures. Back-computed Murphree tray efficiencies are not constant over time, which implies that the equilibrium model should not be used for dynamic simulations.
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    AIChE Journal 41 (1995), S. 1898-1914 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Using asymptotic expansion and numerical analysis, we demonstrate how the step-response ignition time of an automobile catalytic converter depends on the ratio of the reaction rate to the interphase heat-transfer rate, as measured by a key Damköhler parameter χ and the degree of monolith subcooling ŋ.In the region of low reactionrate at smallχ, the normalized ignition time tig scaled bythe homogeneous ignition time from the inlet gas temperature is (tigtig∞) = 1 + 2 χ1/2∣ln( χ1/2/2 η)∣1/2, and the ignition takes place at a thermal front deep in themonolith. At large χ when the reaction rate is high, ignition occursat the leading edge of the monolith with (tig/tig∞) = 2.50 + χ(ln η - 0.34).The delay in ignition time with increasing χ is due to a Taylor-Aris dispersion mechanism induced by interphase heat transfer. Although the small- χ ignition mechanism is faster, its downstream ignition location leads to a very slow upstream propagation of the thermal front that follows ignition. An optimal converter system that ignites in 13 s, 25% of the current value in a standard step-response test, is then designed by placing a small igniter, which ignites by the small- χ mechanism, upstream to preheat the current converter which then ignites by the large- χ mechanism. The length of the igniter is kept small by bypassing 2/3 of the exhaust since, from our theory, tig∞ is independent of the gas velocity.
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    AIChE Journal 41 (1995), S. 1955-1963 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The study of mixed films has become of considerable interest both from theoretical and practical points of view. The π-A isotherms of monostearin-distearin (about 50% 1,3- and 50% 1,2-isomers) mixed films spread on water as a function of emulsifier ratio and temperature were studied in an automated Langmuir-type film balance. When molecules of both emulsifiers are spread on the air-water interface they are packed more closely together than when either emulsifier is present alone, and they enter into some form of association. This association can be demonstrated by surface pressure-area isotherms and by thermodynamic studies. The characteristics of the mixed films, their elasticity and miscibility, which are of interest in emulsion or foam stability are discussed. A molecular model established can explain the interactions between film and subphase molecules and their relationships with variables of the process (pressure and temperature). This model fits the calculated thermodynamic parameters.
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  • 42
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    Notes: Conventional ozonation of recalcitrant organic compounds in wastewater suffers from low transfer rate of ozone into water. The low transfer rate can be enhanced by adding an inert fluorocarbon (FC) liquid immiscible with water but having a much higher solubility for ozone. A novel membrane reactor was studied for the destruction of organic pollutants by using PC liquid simultaneously as a reaction medium and a liquid membrane. The membrane reactor consisted of two sets of microporous and/or non-porous hollow-fiber membranes well-mixed in a cylindrical shell filled with the inert FC liquid. Wastewater was allowed to flow through the lumen of one set of microporous fibers; O3-containing gas flowed through the bore of the other set. Oxidative degradation products get partitioned back into the two mobile phases. Degradation of such pollutants as phenol, acrylonitrile, nitrobenzene, trichloroethylene, and toluene in such a reactor is presented. The kinetics of degradation of each pollutant in the two-phase (aqueous- FC) system were studied using batch and semibatch experiments. Simulation results based on a first-order model to predict the behavior of pollutant degradation in such a membrane reactor are compared with experimental data.
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    AIChE Journal 41 (1995), S. 2029-2039 
    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 analysis and applications of the wave model for longitudinal dispersion are pre-sented. Asymptotic forms of the wave model are considered and analytical solutions of typical linear stationary and nonstationary problems of chemical reactor engineering interest are obtained and compared to those for the Fickian dispersion model. The wave model leads to efficient analytical solutions for linear problems, which in principle differ from the solutions of the Fickian dispersion model; only for slowly varying concentration fields do the soluctions of both models approach each other. Spatial and time moments of the concentration distribution are obtained for pulse-dispersion problems; the first three spatial moments of the mean, variance, and skewness have exact, large-time asymptotic forms in the case of Taylor dispersion. Old experiments that could not be explained with the standard dispersion model are reconsidered and explained: the change with time of the variance of a concentration pulse when the flow direction is reversed and the difference in values of the apparent axial dispersion coefficient and the backmixing coefficient in a rotating disk contactor. The experimental determination of model parameters is discussed.
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    AIChE Journal 41 (1995), S. 2067-2082 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Phenomenologically based model for forth height was developed using the assumption of both vapor-and liquid-continuous zones within the total froth height. The model demonstrates the importance of liquid and vapor rates and determines that the Weber number (and therefore droplet size and surface tension) has little effect on froth height.A composite air/water database including entrainment data for both the spray and froth regimes is used to develop an entrainment correlation as a function of the ratio of tray spacing to froth height (Ts/h2φ) and the average froth density (φ2φ = hL).For conditions resulting in the ratio of liquid inventory to the perforation diameter (hL/dH) 〈4, the height, equation requires an empirical correction for froth height, and entrainment depends onφ2φ.This results from the predominantly vapor-continus nature of the froth. For large values of hL/dH, the theoretical value for h2φ appears adequate and entrainment is essentially independent of φ2φ, since most of the liquid is contained in the liquid-continuous region located far away from the underside of the tray above. In such cases, entrainment is from a light spray on top of the liquid-continuous region, and therefore entrainment depends much less on φ2φ.The differen dependency of entertainment on φ2φ can be used as a method to identify the spray-froth transition. For hL/dH〈2, a spraylikecondition exists; for hL/dH 〉 2, a frothlikecondition exists.The reported dependency of air/water system entrainment on major geometry and operating conditions is described well by the new correlation. Alternate correlations for the non-air/water entrainment data, however, are required. New methods for estimating the impact of entrainment on efficiency are given.
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    AIChE Journal 41 (1995), S. 2131-2139 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Composite metal membranes obtained by supporting thin metallic films on ceramic substrates have good thermal and mechanical stability. The use of a thin metal film increases transmembrane flux, while retaining high permselectivity that is characteristic of metallic membranes. Novel techniques have been developed for preparing metal-ceramic composite membranes. By the appropriate use of osmotic pressure, the microstructure, porosity, and thickness of the deposited metal can be systematically manipulated. Three new procedures are described for film densification and fabrication: (1) the osmotic pressure is used to densify an existing supported metal membrane; (2) densification and growth of the film is managed under the influence of osmotic pressure by using a dilute plating solution; and (3) films of varying porosity are deposited on the ceramic membrane by combining electroless deposition and osmotic pressure. Silver, palladium, and palladium-silver films prepared by these techniques on a commercial alumina membrane (Membralox) are thermally more stable than similar films deposited by conventional electroless plating.
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    AIChE Journal 41 (1995), S. 2140-2149 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Isothermal profiles of the extended meniscus in a quartz cuvette were measured in the earth's gravitational field using an image-analyzing intefferometer thai is based on computaer-enhanced video microscopy of the naturally occurring ineetference fringes. These profiles are a function of the stress field. Experimentally, the augmented Young-Laplace equation is an excellent model for the force field at the solid-liquid-vapor intrfeces for heptane and pentane menisci on quartz and tetradecane on SFL6. Effects of refractive indices of the solid and liquid on the measurement techniques were demonsrrauzd. Experimentally obtained values of the disjoining pressure and dispersion constantswere compared to those predicted from the Dzyaloshiniskii-Lifshitz-Pitaevskii theory for an ideal surface and reasonableagreements were obtained. A parameter introduced gives a quantitative measurement of the closeness of the system to equilibrium. The nonequilibrium behavior of this parameter is also presented.
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    AIChE Journal 41 (1995), S. 2177-2186 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An approximate steady-state method is devised for computing the flow field in a baffled, impeller-stirred tank reactor. The flow field in a cylindrical tank with a 45° pitched-blade impeller rotating at 100 rpm and four stationary rectangular side-wall baffles is simulated using a new approximate steady-state approach. The method provides an alternative to a full unsteady Navier-Stokes simulation. The new steady-state analysis involves accurately defining the geometry of the mixing tank using a multiblock grid technique. The flow is solved from a rotating frame of reference for a single position of the impeller relative to the side-wall baffles. The steady-state numerical results are then spatially averaged and compared with time-averaged data obtained experimentally using laser Dopler velocimetry (LDV). Spatially averaged numerical predictions obtained using this approximate steady-state method for the radial and axial velocity components agree well with the LDV data. The predicted magnitude of the tangential velocity component, however, is higher than the experimentally measured values. Closer agreement of the tangential velocities with experimental values is obtained using a finer grid and it is found that a relatively fine grid is needed for accurately predicting the tangential velocity magnitude. Use of this approximate steady-state method allows designers of mixing vessels to obtain flow-field results for baffled vessels much more efficiently than using full unsteady Navier-Stokes simulations.
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    AIChE Journal 41 (1995), S. 2227-2236 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The growth phenomena, mechanism, and kinetics of naphthalene crystal from supercritical CO2 solution were studies by using a single-crystal technique. Distinct growth features were observed, including the development of individuals from the seeds and the sprouting of plates from the individuals. The surface integration proceeded by two-dimensional nucleation mechanism at face corners and by subsequent spreading of the nuclei. The measured growth rates as functions of supersaturation and solubility were consistent with the derived growth-rate equations, based on the corner nucleation mechanism. In comparison with crystal growth from conventional media, the growth of naphthalene crystals from supercritical CO2 solution is similar to liquid-solution growth as far as growth mechanism and kinetics are concerned.
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    AIChE Journal 41 (1995), S. 2274-2281 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In this work the experimental observations are explained with the aid of a simple air-entrapment model based on the concept of two levels of porosity of fiber mats. A simple model that includes liquid bypassing with initial air trapping, subsequent capillary invasion of regular fiber bundles with air compression, and finally mobilization is proposed to explain air-entrapment phenomena. The simple model successfully rationalizes the observed air trapping and compression during initial liquid-fiber contact. An empirical equation for the mobilization efficiency is adapted to the model to estimate void content. The velocity dependence of the trapped void content predicted by the model is in good agreement with observations.
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    AIChE Journal 41 (1995), S. 1041-1043 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 41 (1995), S. 1061-1070 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Numerical solutions were obtained for the field of velocity in angular forced flow through the annulus between two concentric cylinders of large and infinite aspect ratio with a gap-to-inner radius ratio of 0.05 using a finite-element representation and the FIDAP code. For an infinite aspect ratio, velocity vectors reveal a purely angular motion below a critical Dean number of 37.31 and a secondary motion in the form of pairs of counterrotating vortices above that value. The wavelength of these vortices and the friction factor are correlated in terms of the Dean number. For large but finite aspect ratios a weak secondary motion around the periphery is found to occur below the critical Dean number, while for greater values the vortex at each end of the channel is greatly extended. The computed patterns of flow are in good agreement with prior experimental visualizations as well as with those carried out as part of this investigation. The computed characteristics are also in good agreement with prior theoretical results for limiting cases. The adaptation of the results for flow through an Archimedean spiral is described.
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    AIChE Journal 41 (1995), S. 1113-1121 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Fluid and solid dynamics inside and outside a stable elongated gas bubble in operating conditions corresponding to those of the channeling regime in a fluidized bed are described. It considers the prolate ellipsoid of revolution as a model of the bubble. The results of the analytical model show a significant increase of the fluid velocity inside the bubble with the growth of its relative height. The maximum values of the fluid velocities exist along the vertical axis of the bubble. For the limiting case of a spherical bubble, the fluid and gas performance, such as the existence of a surface of penetration outside the bubble boundaries and circulation zone inside the bubble, are in good agreement with the existing theory.
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    AIChE Journal 41 (1995), S. 1153-1164 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Filtration on horizontal surfaces facing upward is accompanied by sedimentation. Material balances that are based solely on the volume of filtrate and neglect sedimentation flux lead to an understatement of the solids deposited in the cake and potentially large errors in calculated values of the average specific resistance αav. In a gravitational sedimentation experiment with kaolin, the value of αav neglecting sedimentation was 3.75 times greater than the value including the effect of sedimentation. In addition to errors due to neglect of sedimentation, CATSCAN studies show that the slurry concentration above the cake increases with time, contrary to usual assumptions. In a manner similar to batch sedimentation in a closed cylinder, characteristics of constant composition arose from the cake surface. Approximate predictions based on a combination of traditional sedimentation and filtration theory were in accord with the CATSCAN data. Existing filtration theory must be substantially modified to account for the effect of sedimentation.
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    AIChE Journal 41 (1995), S. 1194-1203 
    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 buildup of undesirable sulfur compounds(sulfates and thiosulfates) reduces the scrubbing effectiveness of the LO-CAT I autocirculation sulfur recovery process from acid-gas stream. Among various processes, withdrawing and disposing of a portion of the scrubber solution and replacing this “blowdown” with fresh solution have been the practice in the industry. The application of the electrodialysis system to recycle the blowdown is presented. Experiments were carried out using electrodialysis to separate salts (sulfates and thiosulfates) from the LO-CAT I autocirculation scrubber solution containing organic chelating agents, iron, and various alkali-metal inorganic salts. The results indicated that the electrodialysis was successful in removing 50% of the salts from the scrubber solution with less than 8% loss of organic and 8% loss of carbonates. The fluxes of the undesired salt species were high even at low current densities (200 to 400 A/m2).
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    AIChE Journal 41 (1995), S. 1235-1250 
    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 reaction rate in gas-solid systems can be affected by mechanical stresses that arise as the reaction proceeds. Stresses develop due to differences between precursor and product molar volumes and thermal expansion coefficients. Experimental evidence on the interaction of reaction rate and mechanical stress for the Ti/N2 and Ti/O2 systems is provided. A detailed and consistent mathematical model is developed for the reaction taking place at the constrained precursor/product interface. An elastic formulation for the stresses is adopted, and stress generation due to mismatches in linear thermal expansion coefficients and equivalent volume (Pilling-Bedworth ratio) for the precursor and product are considered. The effect of surface energy, which becomes significant for particle sizes below 1 μm, is also included in the model. Both experimentally and theoretically, conditions exist where the mechanical stresses exceed the strength of the material, leading to mechanical breakdown of the product layer, thus causing a discontinuity in the observed reaction rate. The entire processing history, including the reaction, temperature, and pressure profiles, plays an important role in determining the overall reaction kinetics of the powder.
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    AIChE Journal 41 (1995), S. 1281-1294 
    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 steady formation of fibers in the air-gap wet-spinning process is analyzed, in which solidification of the fiber material is brought about by the diffusional exchange of solvent and nonsolvent in a coagulation bath. The concentration profile within the fiber is determined, and a simple model is given for the change of the material behavior with changing concentration. The material behavior of the uncoagulated spinning solution is described by a constitutive model for viscoelastic liquids that allows the incorporation of a relaxation-time spectrum. The behavior of the solidified fiber is described by a model for rubberlike elastic solids. The effects of variable fiber temperature and skin friction on the fiber motion are also taken into account. The computed velocity profiles are compared to experimental data. These data were obtained by spinning three samples of nominally identical spinning solutions. Even though the theoretically predicted profiles agree well with those obtained with the first two samples, they completely fail to do so for the third. This failure is attributed to the unexpected extreme sensitivity of the model predictions to the width of the dynamic spectrum that is used to infer the relaxation-time spectrum. It is also found that the velocity profile depends rather strongly on the initial conditions for the stress.
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    AIChE Journal 41 (1995), S. 1321-1323 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 41 (1995), S. 1333-1336 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 41 (1995), S. 1368-1374 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Effects of particle properties on the rise of single bubbles in a liquid-solid fluidized bed ared studied by focusing on the particle-shape effect at various bed voidages near incipient fluidization of glass beads and sand particles. Experiments, covering the bubble-size range 6-37 mm and solids holdups as high as 0.94 times that in the packed state, are conducted in a 2-D column to directly observe the possible relationship between the rate and tortuous path of bubble rise. The shape effect, being significant when the close-range (surface-to-surface) interactions between particles are predominant, is appreciable for the relative solids holdups exceeding 0.9. Marked reduction in the bubble rise velocity is observed as the bubble size is decreased below 8 and 12 mm for the spherical glass and irregular sand particles, respectively. This anomalous reduction stems partly from the tortuousness in the rise path and partly from the “hesitation” in the net vertical movement. The former, in particular, is quantified in terms of the tortuosity of the 2-D rise path. The results support the peculiar trend in the rise velocity observed, especially for the sand particles.
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    AIChE Journal 41 (1995), S. 1413-1425 
    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 adsorption of ethane from helium was measured in beds packed with 2.5 μm zeolite crystals and containing either a single hollow fiber or multiple fibers. THe single-fiber experiments indicate that the mass-transfer rate in bends containing zeolite 13X is limited by diffusion across the fiber wall and through macropores. FOr adsorption in single-fiber beds packed with zeolite 4A, mass transfer is limited by micropore diffusion within the particles. Breakthrough curves from beds containign 13X are adequately described with the linear driving force model, while curves from beds containing 4A are consistent with the Rosen model.Breakthrough curves from beds packed with zeolite 13X and containing multiple fibers can be predicted from the experiments with single-fiber beds when the fibers are evenly spaced. When fibers are unevenly spaced, the breakthrough curves are more disperse. Unevenly spaced fibers are the normal case. Even when fibers are evenly spaced, the productivity of hollow-fiber beds is expected to be no greater than that in conventional beds.
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    AIChE Journal 41 (1995), S. 1456-1470 
    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 design method reported here uses extractive crystallization to separate a three-component mixture despite the presence of eutectics. Phase behavior can be classified into six basic types, and six flowsheet structures can handle systems with any of these solid-liquid-phase behaviors. Design equations are formulated for these flowsheet structures, and design variables and constraints are identified. In addition, design issues, such as the choice of solvent, the effect of design variables on recycle flows, and the magnitude of the costs, are discussed.
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    AIChE Journal 41 (1995), S. 1513-1520 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Continuum approximation is often used to treat problems involving reaction mixtures of a vast number of species. Previous studies predicted that in many situations the lumped kinetics of a continuum of reactions, regardless of their kinetics, are of the power law form after a long time. In this article we present experimental support for such asymptotic power law kinetics. The system considered is catalytic deep desulfurization of a petroleum distillate. In addition, a theoretical analysis is made to establish the condition under which the continuum approximation is valid in the long-time limit. The condition turns out not to be very stringent for practical purposes.
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    AIChE Journal 41 (1995), S. 1543-1549 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Special kinetic behaviors in isothermal reactions on heterogeneous catalysts composed of two components with different roles are studied with the focus on hi stabilities that could occur in stirred-tank flow reactors when control of catalytic sites on one component by mobile (spillover) species produced by the other operates. The comprehensive kinetic model involves: (1) generation of spillover species on the second phase, their transfer to the potentially catalytic phase, and their reaction with this acceptor to generate selective sites; (2) the kinetics of the catalytic reaction. We developed a model for selective catalytic oxidation, where catalyst sites change from nonselective to selective under the influence of the control by spillover oxygen. The model is based on the system of differential equations. By integration and iteration to the steady state for each value of the external control parameter under investigation, the oxygen and hydrocarbon reactant consumption, as well as the state of the catalyst, is calculated. These calculations predict bistable selectivity for certain ranges of concentration in the feed. Data on the boundaries of the hysteresis loops as a function of catalyst composition and oxygen partial pressure are discussed, as well as the variation of these hysteresis boundaries as a function of the internal parameters.
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    AIChE Journal 41 (1995), S. 1572-1580 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: One approach to demilitarize solid rocket propellants is treatment with ammonia. Ammonia extracts the oxidizers ammonium perchlorate and HMX, yielding a solid residue that is more suitable for incineration and less sensitive to impact and other modes of accidental initiation. Ammonia treatment of nitroglycerin-containing propellants is complicated by an exothermic reaction between ammonia an nitroglycerin. If not removed, the heat generated by this reaction can cause propellant ignition. To help design safe treatment processes, a model for the ammonia-propellant reaction was developed, which integrates transient energy and species conservation equations to simulate ammonia diffusion, heat generation, and heat flow in a propellant and in the solid residue resulting from ammonia treatment. It was calibrated using residue thickness and thermocouple data for one propellant. The calibrated model was used to predict conditions leading to ignition of thin propellant strips. The results agree well with experimental observations.
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    AIChE Journal 41 (1995), S. 2345-2355 
    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 certain polymer-penetrant systems, nonlinear viscoelastic effects dominate those of Fickian diffusion. This behavior is often embodied in a memory integral incorporating nonlocal time effects into the dynamics; this integral can be derived from an augmented chemical potential. The mathematical framework presented is a moving boundary-value problem. The boundary separates the polymer into two distinct states: glassy and rubbery, where different physical processes dominate. The moving boundary condition that results is not solvable by similarity solutions, but can be solved by perturbation and integral equation techniques. Asymptotic solutions are obtained where sharp fronts move with constant speed. The resultant profiles are quite similar to experimental results in a dissolving polymer. It is then demonstrated that such a model has a limit on the allowable front speed and a self-regulating mass uptake.
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    AIChE Journal 41 (1995), S. 2371-2382 
    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 study of pulsing flow in trickle beds is presented, based on data from two measuring techniques. New evidence on pulse arrangement and propagation in the bed, and data on basic pulse characteristics (frequency, celerity, length, duration) as well as liquid holdup and pressure drop measurements are included. Some of these data, such as the length of the liquid-rich zone of pulses, are not currently available. Two flow regions exhibit different trends of pulse characteristics, “mild” and “wild” pulsing for relatively small and large liquid flow rates, respectively. New findings are compared with previously available data and correlations. An effort to develop new or modify existing generalized correlations is made for the aforementioned quantities.
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    AIChE Journal 41 (1995), S. 2393-2398 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Kinetics of diffusion in a spherical pellet saturated by a sorbate in the presence of an inert component are considered for the case of a step isotherm. A new convective flux inside the pores due to sorption effect has been taken into consideration, and an analytical expression for sorption kinetics is obtained. The convective flux may result in considerable increase in the sorption rate. It is also found that the formula obtained also gives a satisfactory description of sorption kinetics for the case of an S-shaped isotherm.
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    AIChE Journal 41 (1995), S. 2427-2438 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Guildlines for the design of fractional crystallization processes to separate two-and three-solute mixtures are presented. By using solvent addition/removal, stream combination, and cooling/heating, these processes bypass regions of multiple saturation in the phase diagram and recover purse solutes. Design equations are formulated, and the constraints on the design variables are identified. also included is a discussion of the effect on recyle flows of changes in the design variables and an estimate of the cost of a fractional crystallization separation.
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    AIChE Journal 41 (1995), S. 2465-2475 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Six algorithms following single particle trajectories are used to predict the axial dispersion in rolling or slumping flow in a continuous rotary kiln. Models incorporating different physical phenomena show that axial dispersion is affected by the Froude number, L/D ratio, solid fill level, and rolling or slumping layer thickness. The main cause of axial dispersion is segregation of the nonuniform particle size, density and shape. In a rolling bed with uniform particles the rolling layer thickness and the time of roll have to be accounted for in the prediction of the dispersion. The Peclet numbers computed for sold particles with uniform physical properties are of the order of 104. The sold segregated motion may lead to Peclet numbers of the order of 10 - 103, a much larger dispersion. The main obstacle for a-priori prediction of the axial dispersion is lack of a reliable relation between the segregated roll or slump distance and the variation in particles properties, as well as the change in segregation as the flow properties of kparticles are changed during calcination.
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    AIChE Journal 41 (1995), S. 2513-2521 
    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 local time-averaged velocity, the mixed-mean velocity, and the friction factor for fully turbulent flow between parallel plates and in round tubes and concentric circular annuli can be expressed in terms of integrals of the turbulent shear stress, The pressure distribution across a channel can similarly be expressed in terms of an integral of normal stresses. These formulations, which are simple and exact, can be integrated numerically using experimental data, compyted values, or correlating equations for turbulent stresses. Their greatest merit, however, may arise from the insight they provide with respect to the contributions of the fluctuating components of the velocity. For example, for concentric circular annuli such a formulation identifies a difference between the locations of the maximum in the velocity and the zero in the total shear stress. This difference, which has been overlooked in most experimental and semitheoretical investigations, introduces an error of unknown but possibly significant magnitude into all of the results. It also precludes the application of the mixing-length, eddy viscosity and k - ∊ models.
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    AIChE Journal 41 (1995), S. 2522-2536 
    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 hierarchical decision procedure for the synthesis of separation system flowsheets for vapor-organic liquid- aqueous liquid- solid mixtures is proposed. An expanded set of synthesis rules that can be used to obtain a first design is discussed, but the final goal of the procedure is to generate a complete list of separation alternatives (by changing the decisions) that when coupled with short-cut screening techniques, can be used to identify the best few process flowsheets. The procedure is based on a decomposition of the separation system synthesis problem by phase splitting into a vapor recovery system, a solid recovery system, and liquid separation systems. A general superstructure presented for these subsystems includes all of the common unit operations for petrochemical processes. The procedure focuses on the development of a complete flowsheet for the separation system: which separation system recycle loops (in contrast to reactor system recycle loops) are required, as well as interactions among separation subsystems and those between the separation system and remainder of the process. An example presented illustrates the procedure, and the opportunities for pollution prevention at the source are noted.
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    AIChE Journal 41 (1995), S. 2625-2630 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The sensitivity behavior of the fixed-bed catalytic reactors is examined using the pseudohomogeneous two-dimensional model with radial dispersion for the first-order irreversible reaction. The sensitivity criteria developed are tested. The relations between self-similarity and thermal runaway are studied. The pseudoadiabatic type of operation is taken into consideration. The boundaries of the sensitivity region in the space Da - Pe are compared with those predicted by the standard one-dimensional model and the criterion of Hagan et all The sensitivity behavior of the system in the space α - Bi is also discussed.
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    AIChE Journal 41 (1995), S. 2658-2660 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 41 (1995), S. 2661-2663 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 42 (1996), S. 10-22 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Formation of asphalt aggregates and their deposition on the pore surfaces of a porous medium, which alter the structure of the medium and its effective properties, is a critical problem to catalytic and oil recovery and refinery processes. Extensive new experimental data for the amount of precipitated asphalt formed with crude oil and various solvents are presented. Results indicate that, contrary to the previous assumptions, asphalt formation is at best partially reversible. A thermodynamic model based on the Flory-Huggins theory of polymer solutions is used, together with the Soave equation of state, to predict the data. Critical evaluation of the model shows that its predictions do not agree well with our data. As an alternative, we propose a new model that employs a scaling equation, somewhat similar to those encountered in aggregation and gelation phenomena. The scaling function takes on a very simple form, and its predictions are in very good agreement with the data. It also predicts that the onset of precipitation may obey a simple universal equation.
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    AIChE Journal 42 (1996), S. 55-67 
    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 drying and reactions in a liquid coating containing precursors to a random network polymer can give rise to a variety of drying phenomena. Solidification, or gelation, of the polymer may occur before, after, or during the removal of solvents from the coating. Rates of drying and reaction are probed by solving the equations of mass transfer by diffusion along with chemical reaction in one dimension. Solutions to this system of equations are obtained by Galerkin's method with finite-element basis functions and entail large-scale computation. Skinning, or solidification at the surface of the coating while the bulk is still liquid, occurs in thick coatings when the diffusional resistance to drying is significant, that is, at high mass-transfer coefficients. Homogeneous solidification occurs in thin coatings at low mass-transfer coefficients. Drying regime maps represent these solidification phenomena as regions in parameter space.
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    AIChE Journal 42 (1996), S. 96-130 
    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 and ongoing research in the distillation of nonideal mixtures is reviewed focusing on advances in the methodologies for the synthesis, design, analysis and control of separation sequences involving homogeneous and heterogeneous azeotropic towers. Maps of residue curves and distillation lines are examined, as well as geometric methods for the synthesis and design of separation sequences, trends in the steady-state and dynamic analysis of homogeneous and heterogeneous towers, the nonlinear behavior of these towers, and strategies for their control.Emphasis is placed on the methods of computing all of the azeotropes associated with a multicomponent mixture, on the features that distinguish azeotropic distillations from their zeotropic counterparts, on the potential for steady-state multiplicity, and on the existence of maximum and minimum reflux bounds. Important considerations in the selection of entrainers are examined. For the synthesis of separation trains, when determining the feasible product compositions, the graphical methods are clarified, especially the conditions under which distillation boundaries can be crossed and bounding strategies under finite reflux. The application of geometric theory to locate the fixed points, at minimum reflux, is reviewed in connection with homotopy-continuation algorithms for this purpose. The use of homotopy-continuation algorithms, especially for the steady-state simulation of heterogeneous azeotropic distillations, is justified. Methods for phase stability analysis are reviewed in connection with the location of real bifurcation points at phase transitions, an important feature of algorithms for the dynamic simulation of heterogeneous azeotropic distillations.
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    AIChE Journal 42 (1996), S. 187-203 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Discrete-time nonlinear feedback control laws are derived for multivariable nonlinear processes, whose “delay-free” parts are minimum phase. These include mixed error-and state-feedback, error-feedback, and mixed error- and output-feedback laws, which can induce linear input-output closed-loop response. This study is carried out within the framework of the discrete-time globally linearizing control. The broader class of nonlinear processes, in which controlled outputs as well as some other process variables are measured, are also considered. A mixed error- and output-feedback control law is derived for this class of processes. The conditions under which the mixed error- and output-feedback can be applied to a process operating at or around an open-loop unstable equilibrium point are determined. The application and performance of the derived control laws are illustrated by the numerical simulation of a chemical reactor.
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    AIChE Journal 42 (1996), S. 214-231 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The long-time behavior of a reaction mixture containing infinitely many species in isothermal continuous stirred tank reactors (CSTRs) is analyzed and contrasted with that in a plug-flow reactor (PFR). The reaction kinetics considered are irreversible first-order, irreversible coupled pseudo first-order, and reversible first-order. Asymptotic lumped kinetics for the mixture as a whole are developed as a function of feed properties and reactor type. Such lumped kinetics in many cases are of the power law form, with the exponent for a CSTR being lower than that for a PFR. Conditions under which non-power-law kinetics arise are given. Due to the wide spread of reactor residence times, the mixture in CSTRs admits a much richer variety of asymptotic possibilities than in the PFR. The results uncover some behavioral differences and relationships between CSTRs and a PFR for converting complex mixtures such as petroleum distillates or coal liquids.
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    AIChE Journal 42 (1996), S. 258-258 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 42 (1996), S. 319-331 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A unified network model is formulated for predicting effective Fickian diffusivities of condensable vapors in porous media where capillary condensation and adsorption-desorption hysteresis occur. The model unifies the equilibrium theory based on the poreblocking interpretation of hysteresis in the interconnected network of pores and the percolation model of mass transport in the network with randomly interspersed regions for capillary condensation and surface flow. The Bethe network is used to represent the porous medium, and the effective medium theory is employed to obtain the effective diffusivity. Using the information on the connectivity and the positions of the closure points of the hysteresis loop enclosed by the equilibrium primary adsorption and primary desorption isotherms, the concentration dependence of the effective diffusivity is predicted. The model is applied to the systems water vapor-silica gel, water vapor-activated alumina, and literature data. It successfully predicts the concentration dependence of the effective diffusivity in the whole range of relative pressures for systems both with and without a peak in the diffusivity.
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    AIChE Journal 42 (1996), S. 359-368 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A model of simultaneous heat and mass transfer presented describes drying with internal heat generation. Since a liquid expulsion phase is observed, a numerical procedure was developed to account for saturated and unsaturated zones and to model the liquid expulsion. The model was validated by a drainage experiment. An experimental rig was built to conduct microwave drying experiments in well-controlled conditions using capillary porous body (light concrete) as test material. Two types of drying (high and low power) were distinguished, depending on whether or not boiling occurred in the sample. The heat source term in the medium was determined from the experimental results. The numerical results agree with the experimental observations in terms of drying kinetics and transfer mechanisms. This allows a very accurate description of the transport phenomena and the liquid expulsion phase associated with high-power drying.
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  • 85
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    AIChE Journal 42 (1996), S. 277-284 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 86
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    AIChE Journal 42 (1996), S. 259-268 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A simple model was developed to describe the absorption of SO2 in a circulating dry scrubbing (CDS) process, which is a semidry, lime-based, flue-gas desulfurization (FGD) process that utilizes a circulating fluidized bed arrangement for contacting a sorbent with SO2-laden flue gas under “coolside” conditions. The reaction chemistry is thought to be similar to that of spray-drying absorption. The liquid-phase mass-transfer coefficient was successfully modeled as a function of the sorbent particle spacing on the wetted surfaces. Gas-phase mass-transfer resistances were assumed to be insignificant. Due to the high surface area available in a CDS reactor, the evaporation rate of water from the slurry was modeled as “constant-rate” drying according to classic spray-dryer theory. However, the “falling-rate” and “diffusion” evaporation stages were negligible in CDS since sorbent particle bunching at the surface of the slurry is nonexistent.
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  • 87
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    AIChE Journal 42 (1996), S. 271-276 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 88
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    AIChE Journal 42 (1996), S. 298-300 
    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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  • 89
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    AIChE Journal 42 (1996), S. 332-346 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The flows generated in vessels stirred by two Rushton impellers were investigated in two vessels of diameter (T) 100 and 294 mm with impellers of diameter D = T/3 using flow visualization, power consumption, mixing time, and 360° ensemble-averaged and 1° angle-resolved LDA measurement techniques. The flows depended strongly on the clearance of the lower impeller above the base of the vessel (C1), the separation between the impellers (C2), and the submergence (C3) of the upper impeller below the top of the liquid column height (H). When these distances were varied, three stable and four unstable flow patterns were observed. Comparisons between the two LDA techniques showed that while the 360° ensemble-averaged measurements are useful for characterizing the overall flow structure and turbulence levels in the vessel, care must be exercised when interpreting such data, since in the impeller region they include periodic variations in the mean velocity in addition to the turbulent fluctuations. The trailing vortex structure and flow periodicity produced by the Rushton impellers is shown to decay significantly within a cylindrical region of height 1.2D and radius 1.0D centered around the middle of the vessel, when C1 = C2 = T/3. The turbulence structure within this region is anisotropic, while outside this region it might be considered mostly isotropic. The main flow features scaled well between the vessels.
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  • 90
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    AIChE Journal 42 (1996), S. 369-382 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A computer-aided simulator of steady-state two-phase flow in consolidated porous media is developed. The porous medium is modeled as a 3-D pore network of suitably shaped and randomly sized unit cells of the constricted-tube type. The problem of two-phase flow is solved using the network approach. The wetting phase saturation, the viscosity ratio, the capillary number, and the probability of coalescence between two colliding ganglia are changed systematically, whereas the geometrical and topological characteristics of the porous medium and wettability (dynamic contact angles) are kept constant. In the range of the parameter values investigated, the flow behavior observed is ganglion population dynamics (intrinsically unsteady, but giving a time-averaged steady state). The mean ganglion size and fraction of the nonwetting phase in the form of stranded ganglia are studied as functions of the main dimensionless parameters. Fractional flows and relative permeabilities are determined and correlated with flow phenomena at pore level. Effects of the wetting phase saturation, the viscosity ratio, the capillary number, and the coalescence factor on relative permeabilities are examined.
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  • 91
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    AIChE Journal 42 (1996), S. 431-439 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The crystallization of phenanthrene from toluene with carbon dioxide as the antisolvent gas is described. In the GAS process, a pressurized gas is dissolved into a liquid solvent, where it causes a volumetric expansion and lowers the solubility of the solute. Theoretical models are presented for the liquid-phase expansion and the solubility as a function of pressure and temperature. The Nývlt theory for batch crystallization is adapted to predict the pressure profile in the crystallizer needed to maintain a constant supersaturation and growth rate. Generation of seeds is accomplished via a pressure pulse at the saturation pressure. The average particle size of the phenanthrene could be varied from 160 to 540 μm. Creation of seeds doubles the particle size and reduces the coefficient of variation significantly. The residual amount of toluene in the crystals without treatment is approximately 70 ppm. The particles are agglomerates of phenanthrene crystals.
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  • 92
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    AIChE Journal 42 (1996), S. 440-454 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The high throughput and operating cost of the reactor provide the economic incentive in considering the on-line optimization of the LDPE tubular reactor. For an on-line optimization procedure it is crucial to develop a flexible and adaptive on-line parameter estimator, which based on the appropriate measurements from the reactor will adjust certain key model parameters so that the model can capture the actual reactor operation and reliably be used for the real-time optimization of the reactor performance. Various issues involved in developing the on-line estimator for such applications as the mathematical modeling of the reactor, the selection of the adjustable model parameters and reactor measurements, the decomposition of the problem according to the characteristic time constants of various disturbances, and the efficient and robust solution of the mathematical problem are discussed. The tools developed were successfully used on an EXXON high-pressure LDPE tubular reactor. Results from the numerical experiments that are compared with scaled data from a real reactor show that the estimated temperature profiles agree remarkably with those observed at various phases of the reactor operation.
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  • 93
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    AIChE Journal 42 (1996), S. 595-598 
    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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  • 94
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    AIChE Journal 42 (1996), S. 601-612 
    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 previously developed mathematical wetting model is generalized and applied to the following two closely related situations: the spreading of a liquid over a prewet solid surface and the receding contact-line motion with a microscopic residual film, remaining behind the contact line. An analytical expression for the velocity dependence of the dynamic contact angle is derived. Macroscopic characteristics (the dynamic contact angle and drag force) and the flow field corresponding to the spreading of a liquid over a wet solid surface differ considerably from those calculated for a dry surface. Under certain conditions the flow in the reference frame fixed with respect to the contact line has a region with closed streamlines. The region appears due to the flow-induced Marangoni effect, the reverse influence of the surface tension gradient along the liquid-solid interface caused by the flow on the flow, which gives rise to the gradient. The results are compared qualitatively with experimental data.
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  • 95
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    AIChE Journal 42 (1996), S. 683-690 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Simulated countercurrent chromatography is a continuous flow method for separation of binary mixtures or for separation of multicomponent mixtures into two fractions. Countercurrent flow is simulated by moving the feed point past several fixed adsorbent beds at a rate between the single column breakthrough time of each component. The number of columns and the location of the inlet and outlet port were varied to investigate product purity and productivity. Concentration profiles of the effluent product streams were measured. The maximum product concentration exceeds the feed concentration during part of the feed-switching cycle and drops to zero during part of the cycle. Three configurations were tested with the total number of columns varying between three and eight. For the test separation chosen, gaseous propylene and dimethyl ether on Chromosorb 101, high purity (〉 99%) product streams were obtained with an optimal four-column configuration using three desorbent streams.
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  • 96
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    AIChE Journal 42 (1996), S. 700-712 
    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 frequency response method measuring the temperature and pressure of an adsorbent sample determines the mass- and heat-transfer kinetics in adsorbents, especially in zeolites. The temperature of the sample (large crystals or monolayers of pellets) is measured by infrared detection. The main aspects of the in-phase and out-of-phase functions as given by an analytical bidispersed model are described. They depend on characteristic times related to kinetic paprameters. Experimental results on adsorption of water on NaX zeolite (crystals or pellets) show that this method allows heat transfer to be very clearly delineated from mass-transfer modes and the separation of different mass-transfer modes. For a bidispersed sample, macro- and microporous mass-transfer parameters may be obtained with the same sample. Results on a contaminated 5A zeolite-propane system show the presence of mass-transfer resistance at the pellet surface. The infrared temperature measurement associated with the frequency response appears to be powerful in determining kinetic adsorption, and gives more information than the pressure measurement.
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  • 97
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    AIChE Journal 42 (1996), S. 742-752 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: With the growing environmental concern, it is necessary to improve process simulation and develop design tools to account for environmental factors in the synthesis of large-scale chemical processes. A major obstacle in tackling this problem is uncertainties in some of the technical and economic parameters, which lead to uncertainties in design, plant performance, and cost estimates. Further, a conceptual process design involves the identification of an optimal flowsheet structure from many alternatives stituting the “superstructure.” Synthesis and optimization of large-scale processes involving uncertainties often require considerable computational effort. A novel algorithm presented here is based on simulated annealing for the process synthesis of large-scale flowsheets having several configurations and considers uncertainties in the process design systematically. This new “stochastic annealing algorithm,” provides an efficient approach to stochastic synthesis problems by incorporating a penalty term in the objective function and balances the trade-off between accuracy and efficiency based on the annealing temperature. It has been used to study a benchmark synthesis problem in the HDA process. Savings of up to 80% in CPU time has been achieved without significant loss of solution precision with stochastic annealing, compared to simulated annealing with a fixed sample size. It can be applied to analyze efficiently any complex process flowsheet and provide valuable insights into process feasibility based on optimal design, plant performance, and uncertainty issues.
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  • 98
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    AIChE Journal 42 (1996), S. 777-790 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Most advanced control applications rely on good dynamic process models. The performance of the control system depends on the accuracy of the model used. Typically, such models are developed by conducting off-line identification experiments on the process. These identification experiments often result in input-output data with small output signal-to-noise ratio, and using these data results in inaccurate model parameter estimates. Prefilters are used to separate useful information from the noise in the input-output data and to improve parameter estimates. A systematic design procedure for selecting a prefilter using discrete wavelet transforms is presented. The design procedure provides explicit information on the compromises in prefilter design, interpreted in terms of parameter variance and bias. The prefilter design procedure is then applied to identify a second-order output error model.
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  • 99
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    AIChE Journal 42 (1996), S. 820-828 
    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 new application of nuclear magnetic resonance imaging (MRI) techniques for characterizing fractures and flow in fractured media is investigated. Specifically, a relaxation-weighted imaging technique is used for selectively highlighting either fracture or porous matrix regions. Many advantages over conventional spin-density MRI techniques for characterizing fractured media are demonstrated. Its use to speed image acquisition is also demonstrated. In addition, a multislice profile imaging technique is used to investigate imbibition and drainage displacement experiments in fractured porous media. These images demonstrate that the fractures can have profound effects on the fluid distributions in multiphase flow.
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    AIChE Journal 42 (1996), S. 861-875 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A primary constituent in high-temperature (120-140°C) milk fouling residues is calcium phosphate in the form of calcium phosphate dihydrate (brushite, CaHPO4 · 2H2O) and hydroxyapatite [Ca5(PO4)3OH]. The removal of these mineral-rich deposits from stainless steel occurs by dissolution and mechanical cleaning. This research uses a novel solid scintillation technique to noninvasively and continuously investigate the removal of P32-labeled mixtures of calcium phosphate from inner surface of stainless steel tubes. The proposed mass-transfer model suggests that the film is initialy removed by dissolution, when compared to the experimental results. An alternative first-order model presented includes the effects of the solvent flow rate and solvent pH on decontamination rates. This model agrees with the experimental cleaning data over the range of pH and flow rates studied.
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