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  • 1995-1999  (3,058)
  • 1990-1994  (6,438)
  • Chemical Engineering  (4,929)
  • Engineering General  (4,567)
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  • 101
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1403-1413 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Industrial design of electrostatic precipitators is based on the transport theory developed by Deutsch (1922), which assumes that transverse turbulent mixing is effective enough to maintain the concentration profile uniform throughout the cross section (i.e., turbulent diffusivity is assumed infinite). To improve understanding of turbulent particle dispersion under the influence of electrostatic forces, a database on particle trajectories was first generated, based on the flow field from a direct numerical simulation of a plate-plate precipitator (Soldati et al., 1993). The effect of various parameters, such as particle size, charge and particle migration velocity, on dispersion and collection efficiency was investigated. Results show that particle concentration profiles are not uniform due to finite values of “turbulent diffusion” coefficient. The simulations indicate that the early stages of particle collection are controlled by particle migration velocity, while final stages are controlled by turbulence diffusion mechanisms.
    Additional Material: 12 Ill.
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  • 102
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1414-1425 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A computed tomographic scanner was developed for imaging gas-holdup distributions in two-phase flow systems such as bubble columns and fluidized beds. The scanner has been used to study the effects of various operating parameters (such as column diameter, superficial gas velocity, and distributor type) on the gas holdup and its distribution in an air-water bubble column. The experimental investigation shows that the column dimensions have no significant effect on the void fraction when the column diameter is greater than 0.15 m. Differences in the holdup distribution due to the kind of distributor used are significant only at low gas flow rates. Surface tension of the liquid has a profound influence on the gas holdup and its distribution.
    Additional Material: 13 Ill.
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  • 103
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1545-1550 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Homogeneous thermal cracking of ethane, which is an endothermic and hence energy-intensive process, was carried out in the presence of limited O2 under different process conditions (at 600°-850°C; O2/ethane ratio of 0-0.2; H2O/ethane ratio of 0-3.3; and space velocity of 2,000-11,000 h-1). The influence of a sulfur additive in the feed and reactor material on the process performance was also investigated. Noncatalytic oxycarcking of ethane in the presence of limited O2, greatly enhances not only the total conversion of ethane but also the conversion of ethane by purely thermal cracking. This process also occurs at a much lower contact time than that required to achieve the same conversion for the thermal cracking process. Also, both the exothermic oxidative conversion and the endothermic thermal cracking of ethane occur simultaneously, which makes this process very energy-efficeint, with a drastic reduction in external energy requirement and coke formation. By manipulating the process conditions, particularly the temperature and O2/C2H6 ratio, the overall process can be made almost thermoneutral, mildly exothermic, or mildly endothermic.
    Additional Material: 5 Ill.
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  • 104
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1717-1726 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Cylindrical internal reflectance infrared spectroscopy (CIR-FTIR) was used for the determination of the transport properties of hydrocarbons in zeolite L at high temperatures and pressures. This was the first time that the intracrystalline diffusivity of hydrocarbons in microporous media could be determined under supercritical conditions by using a dynamic technique. The study investigated the self-diffusion of n-heptane, the counterdiffusion of n-hexane and 1-hexene, and the codiffusion of n-heptane and pyxlene in zeolite L under subcritical and supercritical conditions. The diffusion time constants obtained for the single and binary systems showed that the diffusion within the pore was reduced significantly under supercritical conditions (i.e., liquidlike behavior) as the hydrocarbon density within the pore was increased.
    Additional Material: 12 Ill.
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  • 105
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1763-1784 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A nonlinear model-predictive control scheme based on the autoregressive-plus Volterra model is proposed. A “plant-friendly,” yet persistently exciting, input sequence is designed for model identification. A second feature of this work is that the control action is determined by solving a less computationally burdensome nonlinear programming problem than the optimization problems associated with Newton-type controllers and polynomial ARMA model nonlinear MPC. A third contribution is that semiglobal closed-loop stability conditions are derived and are shown to be less conservative than those previously published. The control scheme is shown to outperform a feedback strategy using proportional integral control and a linear model-predictive control design for the control of two polymerization reactor case studies. The complex features of the latter case study [multivarible (3 × 3), recycle loop, high-order (24) dynamics] motivate the applicability of this approach for industrial problems.
    Additional Material: 20 Ill.
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  • 106
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 1797-1812 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: ZSM-5 zeolite membranes with reproducible properties were prepared by in-situ synthesis on porous α- and γ-alumina tubular supports and characterized by XRD, SEM and electron microprobe analysis. Single-gas permeances for H2, CH4, N2, CO2, n-butane, and i-butane increase over some temperature range, but some gases exhibit maxima or minima. The highest ideal selectivities at room temperature are 299 for N2/SF6, 392 for H2/n-butane, and 2,820 for H2/i-butane. These membranes can separate n-butane/i-butane, H2/n-butane and H2/i-butane mixtures. All n-butane/i-butane separation selectivities have maxima as a function of temperature and are higher than ideal selectivities because n-butane inhibits i-butane permeation. Thus, separation is not by size selectivity, but is due to pore blocking. Temperature depenencies of single-gas permeances and separation selectivities depend strongly on the location of zeolite crystals and the location is determined by preparation procedure. Ideal selectivities also depend strongly on the preparation procedure. When the zeolite forms a continuous layer on the inside surface of the support tubes, pure i-butane permeates faster than pure n-butane so that the single-gas permeances are not determined just by molecular size. The i-butane permeance also increases much more with temperature than the n-butane permeance. The permeation behavior may be the result of permeation through nonzeolitic pores in parallel with zeolite pores. When zeolite crystals are dispersed throughout the pores of α-alumina supports, permeances are lower and gas permeation and separation properties are quite different. Ideal selectivities are lower, pure n-butane permeates faster than i-butane, and the permeances increase much less with temperature. Separation selectivities are lower but can be maintained to higher temperatures.
    Additional Material: 19 Ill.
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  • 107
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2773-2784 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A quantitative understanding of the thermochemistry of silicate solution systems is necessary for the design, optimization and control of sol-gel, colloid and zeolite preparations. This review is intended to be a compendium of ready information for the growing number of chemical engineers active in solution-based materials synthesis. Experimental measurements of silica solubility, silicate speciation and silanol deprotonation in aqueous solutions are summarized and critiqued. The thermochemical properties of monomeric and dimeric silicate anions are also assessed. The trends that are then evident are compared with expectations from simplistic gas-phase molecular orbital calculations to illustrate the importance of solvation. Finally, the equilibrium behavior of simple silicate oligomers is rationalized, and the future direction to quantitative modeling of the behavior of more complex oligomers is suggested.
    Additional Material: 9 Ill.
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  • 108
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2785-2792 
    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 fluorescence properties of inorganic and organically-modified rare-earth-doped sol-gel silica are presented. Eu3+-doped ormosils were prepared from Si(OCH3)4 and CH3Si(OCH3)3, (CH3)2Si(OCH3)2, (CH3)2Si(OC2H5)2, or (n-C3H7)Si(OCH3)3 in various proportions. Er3+-doped ormosils were prepared using Si(OC2H5)4 and CH3Si(OC2H5)3, (CH3)2Si(OC2H5)2 or C2H5Si(OC2H5)3. Gels derived from Si(OCH3)4 were also doped with the fluorinated Eu3+ precursors Eu(fod)3, (CF3SO3)3Eu, and (CF3CO2)3Eu·3H2O. The effect of metal ion codopants, which are known to inhibit clustering of Eu3+ in sol-gel silica, on Er3+ fluorescence is also considered. Fluorescence line-narrowing studies of Eu3+-doped samples indicated that significant Eu3 clustering occurs in both the ormosils and fluorinated precursor compositions. Lifetime measurements of the Eu3+-and Er3+ -doped ormosils showed longer lifetimes at low heat treatment temperatures relative to purely inorganic sol-gel silica, but no significant difference remained in fully densified samples. The longest lifetimes were observed for samples doped with the fluorinated precursors, indicating that the fluorinated ligands are effective at reducing the water content in densified gels.
    Additional Material: 5 Ill.
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  • 109
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2802-2808 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Zeolite fiber, film, and monolith were prepared by using nanosize titanium silicalite (TS-1) crystals. Films and fibers of TS-1 zeolite were optically transparent, which might be important for advanced optozeolitic materials. A permeation result of gases on monolith indicates that the gas permeation is governed by the Knudsen mechanism. All types of TS-1 zeolites manufactured in this work are observed to be MFI structure with an orthorhombic symmetry. These results suggest that nanosize zeolites have potential to allow morphological design with applications for advanced functional materials.
    Additional Material: 9 Ill.
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  • 110
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 111
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    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 3133-3146 
    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 slide coating of photographic films, liquid layers flow down an inclined plane, across a small gap under a pressure differential (vacuum), and onto a fast-moving substrate. Process interruptions to allow splices of adjoining rolls of substrate to pass through the coater result in significant waste. Coating over splices fails due to air entrainment and/or two free-surface flow instabilities during the necessary gap widening: (1) standing waves (ribbing) or rupture of the liquid bridge when vacuum is kept high or (2) lateral contraction when vacuum is lowered. The problem of coating over splices is solved here by reducing it to a fluid-mechanical stability problem. First, air entrainment was eliminated by serrating the splice trailing edge and lateral contraction by prewetting the substrate with liquid streams. Avoiding rupture of the liquid bridge then reduces the problem to finding the vacuum at which the bridge becomes unstable to small disturbances. This “critical” vacuum is found by finite-element stability analysis of the quasi-steady 2-D free-surface flow to small 2-D and 3-D disturbances, direct tracking of critical points, and verification by solving the transient 2-D skip-out process. Three modes of failure are predicted if the vacuum is not sufficiently reduced with gap widening. Implementation of a computed vacuum strategy in a production line gave sufficient latitude for coating over imprecise splices.
    Additional Material: 19 Ill.
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  • 112
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 113
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    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2393-2404 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Direct numerical simulations were used to investigate turbulence structure and scalar transfer across a shear-free, nonwavy gas-liquid interface (free surface) in stably stratified turbulent flows. These simulations solve the Navier-Stokes and thermal-energy conservation equations, using a finite difference approximation. The relation between the turbulence structure in the stably stratified turbulent boundary layer and organized motion near the free surface are discussed. In addition, scalar transfer across a free surface is investigated by solving a passive scalcr conservation equation after both velocity and temperature fields are fully developed. The effects of stable stratification on the scalar transfer process in a region very close to the free surface are also discussed.
    Additional Material: 15 Ill.
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  • 114
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2424-2431 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A laser Doppler anemometer was used to measure velocity components for the flow of a Newtonian fluid in a reversing section of a pilot-scale corotating twin-screw extruder. Measurements were made at a fixed axial position in the intermeshing (nip) region and the translational region (áway from the nip). Tangential and axial velocity profiles reached a maximum in the middle of the screw channel, indicating pressure flow. Leakage flow through the gaps between screw flights and backflow toward the hopper were observed only in the nip region. No reversal of flow was detected in the translational region. Measured velocity profiles showed substantially higher shear rates in the reversing section of the screw as compared to those in the forward-conveying section.
    Additional Material: 9 Ill.
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  • 115
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2415-2423 
    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 miscible displacement of aqueous lignin solutions (model black liquor) by water from beds formed from glass beads was studied as a function of the presence of cationic polymer in the wash water, bed structure, lignin concentration, and superficial flow rate. The displacement behaviors in homogeneous beds formed from fine beads (121 μm) were compared with results of experiments using a channel bed consisting of a bed formed from fine beads surrounding a channel of coarse beads (638 μm) running the length of the bed in the flow direction. Washing efficiencies, defined as the fraction of lignin removed when one pore volume of eluate was collected, were 84-93% for homogeneous beds washed with water compared with 31-33% for the channel bed; the range in efficiencies reflects the influence of other variables. The presence of cationic polymer in the wash water enhanced the washing efficiency by 1.7 to 2 times with a corresponding 20 to 35% decrease in the permeability of the central channel in the channel bed. The improved washing with polymer was due to selective plugging of the central channel with precipitate formed from complex formation between anionic lignin in the black liquor and the cationic polymer. Breakthrough curves obtained from 12 microconductivity probes located throughout the bed showed that mixing of lignin in the black liquor and the cationic polymer. Breakthrough curves obtained from 12 microconductivity probes located throughout the bed showed that mixing of lignin solution (high conductivity) with wash water (low conductivity) in the displacement front, as expressed by a mixing length, was a maximum in the coarse bead channel and was decreased when the wash water contained cationic polymer.
    Additional Material: 9 Ill.
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  • 116
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2471-2478 
    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 selectivity, Si, j = (Xi/yi)/(xj/yj), is examined in a 1-D model of a mixture of hard rods adsorbing on a linear substrate. The adsorbed components are characterized by their length, li, and equilibrium constant, ki. We derive an expression for the bulk-phase pressure Po, for which there is no separation of components i and j, S,i, j = 1, in terms of these parameters. The selectivity of the smaller component always increases with the bulk pressure, which results in a selectivity reversal if, as is usually the case, the larger component is more strongly adsorbed at low surface coverages. In a binary mixture, when P 〈 Po, the selectivity of the smaller component decreases with increasing bulk-phase mole fraction, y1, while for P 〉 Po, the reverse is true. The effect of varying the molecular parameters on the selectivity is also studied.
    Additional Material: 10 Ill.
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  • 117
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    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2456-2470 
    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 isotope exchange technique (IET) can be used to simultaneously measure multicomponent gas adsorption equilibria and self-diffusivities of the components in a single isothermal experiment without disturbing the overall adsorbed phase. An experimental protocol for the IET and corresponding data analysis procedures is described. Isotherms and self-diffusivities for adsorption of N2 as a pure gas were measured on commercial samples of a carbon molecular sieve and a 4-Å zeolite using IET, as well as those of O2 and N2 from their binary mixtures. The carbon molecular sieve did not exhibit thermo-dynamic selectivity for air separation, but had a kinetic selectivity of O2 over N2 Mass-transfer resistances for self-diffusion of N2 and O2 on the carbon molecular sieve were controlled by pore mouth restrictions in the carbon, but those for adsorption of N2 into the 4-Å zeolite by Fickian diffusion inside the adsorbent. A linear driving force model described the uptakes of N2 and O2 in the carbon molecular sieve. The Fickian diffusion model described the N2 uptake in the 4-Å zeolite. Mass-transfer coefficients for both O2 and N2 on the carbon molecular sieve increased linearly with increasing gas-phase partial pressure of these gases, and the pressure of O2 did not affect mass-transfer coefficients for N2. The self-diffusivity of N2 in the 4-Å zeolite decreased with increasing adsorbate loading.
    Additional Material: 13 Ill.
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  • 118
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2488-2508 
    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 concept of standing concentration waves is introduced to derive design equations for continuous moving bed (CMB) processes. For linear isotherm systems, simple equations are derived from the analysis to link product purity and recovery to zone lengths, bed movement velocity, flow rates, column capacity factors, and mass-transfer coefficients. Once product purity, recovery and feed flow rate are specified for a given system, the zone flow rates and bed movement velocity that provide the highest throughput and the lowest solvent consumption can be determined from the solutions. In a given system, there is a trade-off between product purity and throughput. If bed volume and product purities are fixed, the longer the zone lengths, the higher the throughput. Simulations based on a linear driving force model that considers axial dispersion and lumped film and intraparticle diffusion are used to compare the column profiles and effluent histories of CMB and simulated moving bed (SMB). A numerical algorithm is introduced to allow simulation of both CMB and SMB operations using the same program. The comparison shows that the design equations derived for CMB systems are applicable to SMB systems. Finally, the standing wave solutions are used to analyze an experimental SMB system from the literature (Ching et al., 1991). Simulations agree closely with the data and the predictions of the theoretical analysis.
    Additional Material: 17 Ill.
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  • 119
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2765-2772 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new molecular dynamics (MD) code was developed to simulate the continuous deposition process of various molecules on substrates. In this methodology, various molecules can be deposited over substrate surfaces one by one in regular time intervals with definite velocity. It enables us to simulate homo- and hetero-epitaxial growth process as well as cluster formation process on various substrates. This new MD code has been already applied to study the homoepitaxial growth and Au cluster formation processes on MgO(00l). This article compares such phenomena as growth mode, temperature effect, and influence of surface defects in the homoepitaxial growth and Au cluster formation processes on the MgO(001), based on previous results. The continuous deposition process of MgO molecules was simulated. A 2-D smooth MgO layer without any defects was formed at 1,000 K, which was not realized at 300 K. High temperature is favorable for the complete layer-by-layer homoepitaxial growth. The deposition process of Au atoms on the Mg(001) differed significantly from that of MgO molecules. A 3-D hemispherical Au cluster was constructed on the MgO(001) and low temperature was found to be desired for the fabrication of highly active supported Au catalysts. The origin of the different growth mode and the different temperature effect in the homo-epitaxial growth and Au cluster formation on the MgO(001) was clarified.
    Additional Material: 6 Ill.
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  • 120
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2809-2819 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It was, for the first time, demonstrated by means of FTIR, EXAFS, XPS, and XRF techniques that thermally stable Co-Mo binary sulfide clusters were synthesized in NaY zeolite cavities using Co and Mo carbonyls as precursors. The hydrodesulfurization (HDS) and hydrogenation activities of the intrazeolite nanocomposite sulfide clusters were examined as a function of composition. It was found that the highest HDS activity was attained at Co/Mo ≃ 1 (2 Mo/super cage or 12 wt. % Mo) and that the Co sites of the clusters were responsible for the reactions. The composition of the catalytically active intrazeolite Co-Mo sulfide clusters was implied to be Co2Mo2S6. The present intrazeolite nanostructure approach strongly suggested that the Co-Mo binary sulfide formation played a prominent role in the catalytic synergy generation. Metal carbonyl techniques were used in the preparation of intrazeolite Fe-Mo binary sulfides.
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  • 121
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2827-2831 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Cross-linkable organic NLO chromophore called DRS was chemically incorporated into silica matrices using the sol-gel process. A number of electrically poled DRS/silica matrix systems were studied to elucidate the relaxation of the oriented organic chromophore by following the decay of UV absorption as a function of time and temperatures. The value of the second harmonic coefficient d33 was 47 pm/V for the DRS/silica matrix films (0.4 μm thickness). From the dramatic decrease in the UV absorption after poling at 80°C, it is speculated that the DRS may act as a liquid crystalline mesogenic group and is effectively oriented in poling at the phase (nematic) transition temperature (80°C). This argument was substantiated by investigating the phase behavior of DRS itself using both DSC and a polarized optical microscope. The DRS/silica system contained the ideal matrices to retain the oriented chromophore because of optical clarity, thermal stability and effective poling at the nematic liquid crystalline phase.
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  • 122
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2844-2848 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Ba(Zr, Ti)O3 [BZT] thin films were prepared for potential use as a decoupling capacitor for a multichip module (MCM). The crystal structure of BZT thin films on Pt(100)/MgO(100) and MgO(100) deposited from Ba(Zr0.2Ti0.8)O3 powder targets has a perovskite structure and is strongly (100) oriented. The crystal structure of BZT thin films on Pt(111) coated substrates differ from that of Pt(100)/MgO(100) and MgO(100) substrates. The degree of preferred (100) orientation on Pt(111)/SiO2/Si increased with increasing deposition temperature. We obtained a maximum dielectric constant of 150 at 600°C deposition. The loss tangent, leakage current and temperature dependence of capacitance of these BZT thin films were very small.
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  • 123
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2849-2856 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Piezoelectric ceramic/polymer composites, also known as piezocomposites, have been developed over the past two decades for electromechanical transducers to be used in both military and civilian applications. Recently, the thrust in these transducers is toward high operating frequencies, requiring fine-scale (〈200-μm ceramic-phase dimension) piezocomposites. Methods for processing these fine-scale piezocomposites are discussed. Current capabilities, as well as strengths and weaknesses of each method, are compared. The fundamentals of medical imaging and the importance of spatial scale in composite performance are reviewed. Several processing methods demonstrated composites with fine-scale ceramic phases (〈50 μm), and others have shown the potential to form composites with a ceramic scale of under 20 μm.
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  • 124
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    AIChE Journal 43 (1997), S. 2874-2877 
    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 preparation of LaNiO3, La4Ni3O10, La3Ni2O7-δ and La2NiO4 via La-methoxy-ethanolato-Ni(acac)2 precursor was investigated. From these precursors films, fibers and powders were prepared and heat treated to form LaNiO3 at temperatures as low as 750°C with a heating time of 4 h. The formation of La4Ni3O10 and La2NiO4 was complete at 1,000°C, for 4 h, while monophasic La3Ni2O7 required heating to 1,150°C, for 1 h. Pathways yielding various phases were also discussed briefly. The techniques used in this study are TGA, mass-spectroscopy, SEM-EDS, TEM-EDS, powder-XRD, and FT-IR spectroscopy.
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  • 125
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    AIChE Journal 43 (1997), S. 3070-3084 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In coal-fired combustion systems solid calcium species may be present as ash components or limestone added to the combustion chamber. In this study heterogeneous reactions involving HCN over seven different limestones were investigated in a laboratory fixed-bed quartz reactor at 873-1,173 K. Calcined limestone is an effective catalyst for oxidation of HCN. Under conditions with complete conversion of HCN at O2 concentrations above about 5,000 ppmv the selectivity for formation of NO and N2O is 50-70% and below 5%, respectively. Nitric oxide can be reduced by HCN to N2 in the absence of O2 and to N2 and N2O in the presence of O2. At low O2 concentrations or low temperatures, HCN may react with CaO, forming calcium cyanamide, CaCN2. The selectivities for formation of NO and N2O from oxidation of CaCN2 is 20-25% for both species. The catalytic activity of limestone for oxidation of HCN decreases with increasing degree of sulfation. Simultaneously the selectivity for formation of NO decreases while tht for N2O increases. The catalytic activity of sulfated limestone in-creases with decreasing SO2 concentration, indicating a competition between SO2 and HCN for sites on the surface. The results indicate that heterogeneous oxidation of HCN is important in calciners and fluidized-bed combustors with limestone addition or when burning coals with an ash with a high catalytic activity.
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  • 126
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    AIChE Journal 43 (1997), S. 3161-3174 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Plantwide control involves the systems and strategies required to control an entire chemical plant consisting of many interconnected unit operations. A general heuristic design procedure is presented that generates an effective plantwide control structure for an entire complex process flowsheet and not simply individual units. The nine steps of the proposed procedure center around the fundamental principles of plantwide control: energy management; production rate; product quality; operational, environmental and safety constraints; liquid-level and gas-pressure inventories; makeup of reactants; component balances; and economic or process optimization. Application of the procedure is illustrated with three industrial examples: the vinyl acetate monomer process, the Eastman plantwide-control process, and the HDA process.
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  • 127
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    AIChE Journal 43 (1997), S. 3193-3204 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In solving large simulation problems using Newton's method, a large sparse linear system Ax = b has to be solved. The cost of solving its problems can dominate the overall solution cost of the problem. Current approaches of reducing these costs are reviewed, and then a new algorithm for preordering the sparse matrix A is described that is based on the hierarchical structure provided by an object-oriented description of many recent modeling systems such as ASCEND, gPROMS, DIVA, and Omola. Particularly, rapid preorderings are obtained to support interactive manipulation of models and efficient solutions in automatic process synthesis algorithms, two applications where the preordering cost will be spread over only a few factorizations. With a factorization routine that permits a-priori reorderings (LU1SOL), this algorithm produces order of magnitude reductions in analysis and factoring times as well as in fill and operation count over our previous experience. The time to factor the 50,000 Newton equations for a highly recycled ethylene plant model is of the order of a few seconds on a conventional workstation. Abstracting and applying the fundamental concepts of this algorithm made it possible to improve the performance of the ma28 code significantly. This approach makes solution speeds competitive with and generally more consistent than codes considered the state-of-the-art (ma48 and umfpack 1.0).
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  • 128
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    AIChE Journal 43 (1997), S. 2641-2649 
    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 morphological evolution of flame-generated “primary” spherules and inorganic aggregates was studied at low particle volume fractions [O(10-1 ppm)] in a welldefined/characterized laminar nonpremixed combustion environment which produces particle heating rates of 104 K/s. Pure Al2O3 particles synthesized in an Al(CH3)3 (TMA-) seeded atmospheric pressure laminar counterflow diffusion flame “fueled” with CH4/O2/N2 were used as the model material/combustion system. Experimental techniques included spatially resolved laser light scattering (LLS) and thermophoretic sampling/transmission electron microscopy. Local aggregate morphology was characterized in terms of spherule (“grain”) size, aggregate size, aggregate shape and fractal structure. Effects of flame temperature and TMA concentrations on particle inception location, sizes and morphology studied systematically were interpreted based on parallel theoretical studies. LLS signals and TEM images show particle/aggregate size and morphology evolution as a result of two competing rate processes. Mean spherule diameters prior to high-temperature coalescence are explained in terms of the strong size dependence of nanoparticle restructuring kinetics due to surface melting, even at 500 K. Mean fractal aggregate sizes reached only 15-27 spherules near a local temperature of only 1,250 K. Final particulate products were isolated spherical particles resulting from complete “collapse” of the aggregates in an interval of only 24 ms immediately upstream of the maximum gas temperature (2,280 K). Experimental results are compatible with the characteristic times governing each participating “unit” rate process. Some of these methods can be applied in controlling the larger-scale synthesis of valuable nanopowders and guide rational extensions into the domain of turbulent nonpremixed combustors generating ultrafine particles of tailored composition and morphology at high mass loadings.
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  • 129
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    AIChE Journal 43 (1997), S. 2688-2697 
    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 chemical reaction mechanism and fine particle generation during atmospheric pressure chemical vapor deposition with the tetraethylorthosilicate/ozone system were studied experimentally and theoretically for a flow-type vertical-tube reactor. For the thermal decomposition of ozone, numerical simulations obtained using reaction rate constants for a batch reactor explained experimental results well. The activation energy of chemical reaction between TEOS and the oxygen radical, O· was evaluated from the particle generation rate (2.18 × 105 J/mol). Particle population balance equations, based on the simplified reaction coagulation model, were coupled with equations for the thermal decomposition of ozone and chemical transformations of TEOS and solved numerically. Calculation results for particle number concentration and size agreed with experimental results for temperatures below 430 K. For temperatures above 430 K measured concentrations agreed well with calculated values, but measured sizes were significantly smaller than calculated sizes. Thermal desorption spectra from particles generated at 423 K revealed a peak from C2H4 at ∼ 800 K, presumably from ethoxy groups. This emission explains, at least in part, the observed decrease in particle size at high temperatures.
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  • 130
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    AIChE Journal 43 (1997), S. 2724-2730 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mordenite (MOR) and ferrierite (FER) membranes without any pinhole and crack were synthesized by a vapor-phase transport method. The permeance of H2, He, CH4, N2, O2 and CO2 was determined at 290-400 K, which showed minimum with increasing temperatures for most cases. In the parallel diffusion model was proposed, molecules adsorbed in a micropore are assumed to diffuse in parallel through the central region of the pore and along the wall region of the pore. This parallel diffusion model accounts for the effect of pore size of MOR and FER on the permeation and expresses the experimental data well. The interaction between gas molecules and pore walls are evaluated for each gas.
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  • 131
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    AIChE Journal 43 (1997), S. 2715-2723 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Asymmetric membranes consisting of palladium, ruthenium and platinum deposited on the surface or inside the pores (average size, 200 nm) of a tubular alumina membrane were prepared by the chemical vapor deposition (CVD) technique. Sublimation and decomposition temperatures of their acetylacetonato complexes used as metal sources for CVD were important factors in preparing the membranes selected for hydrogen separation. Among the membranes prepared by CVD, the palladium membrane gave the highest flux of hydrogen and was about 1.6 times higher than a dense palladium membrane with a thickness of 4.5 μm prepared by an electroless plating technique. The hydrogen permeation through the membranes prepared by CVD are related to the surface diffusion of spillover hydrogen.
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  • 132
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The variation of crystal system and conduction behavior of perovskite superconductor, BaPb0.75Bi0.25O3-δ, with oxygen deficiency was studied. The crystal system of BaPb0.75Bi0.25O3-δ changed from orthorhombic through tetragonal to pseudo-cubic as δ increases. The superconducting transition was observed in the specimens with the orthorhombic phase. Oxygen-deficient specimens with tetragonal or pseudo-cubic symmetry did not show a superconducting transition. The increase in electrical resistivity was also observed with an increase in δ. which suggested decrease of electron carrier mobility with the increase in δ. This effect of oxygen deficiency on conduction behavior of BaPb0.75Bi0.25O3-δ showed contrast with those of the superconducting cuprates, in which carrier concentration is affected instead of carrier mobility. The difference in the effects of oxygen deficiency on conduction behavior could be attributed to the difference of crystal structure between BaPb0.75Bi0.25O3-δ and superconducting cuprates.
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  • 133
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    AIChE Journal 43 (1997), S. 145-156 
    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 dynamics of semibatch reactors is often neglected in the literature despite their industrial importance. This article analyzes the stability and dynamic behavior of semibatch polymerization reactors operated according to a flow scheduling strategy designed to impart a steady-state nature to the dynamics of these essentially transient reactors. It can also improve the operation of these reactors, especially the quality of the polymer produced (such as molecular weight distribution and polymer composition). In the proposed strategy of flow rate scheduling, the intensive states of the reactor can be made to reach steady-state values. A comparison of the dynamics of the proposed and classical operating strategies illustrates this possibility. Further dynamic analysis reveals the emergence of phenomena characteristic of continuous operation in a CSTR. Examples are multiplicity of the trajectories, limit cycle oscillations, as well as nonhomogeneous oscillations belonging to a period doubling cascade. Operation in a sequential semibatch mode is discussed, as well as the importance of selecting parameters for the fillup and discharge operation. In this mode of operation either periodic or chaotic behavior is obtained. The effect of both on polymer properties is studied in detail.
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    AIChE Journal 43 (1997), S. 273-276 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 135
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    AIChE Journal 43 (1997), S. 317-327 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mechanistic model was developed to predict pressure drop and flooding in packed columns equipped with corrugated packing of the regular type. It was developed after considerating the interaction of falling liquid film with the gas phase, based on mass-and momentum-conservation equations. Among the most common structured packings, the behavior of the Mellapak and BX types was analyzed. The aim of this work is to demonstrate how mechanistic models, developed for simple geometry, can also be used to compute pressure drops in cases where the geometry is more complex, as with a structured packing. This approach, based on the geometric characteristics of the packing and measurable parameters such as liquid holdup, enables the development of a basic model by limiting the number of adjustable parameters, which are numerous in all the available models. Because of its nature, this model is extremely easy to extend to different types of structured packings.
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  • 136
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    AIChE Journal 43 (1997), S. 388-397 
    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 thermodynamically consistent, multimodel approach for the prediction of mixture adsorption equilibria from pure-component adsorption isotherms is described. The ideal adsorbed solution (IAS) model is employed at low surface coverage, where potential attractive forces tend to govern adsorption behavior. An energetically quasi-homogeneous version of the Langmuir-Freundlich (LF) model is proposed at high coverage, where lateral adsorbate interactions and finite-adsorbent geometric constraints tend to homogenize such attractive forces. The classical LF model is used for intermediate coverage, where both energetic attractive and geometric constraining forces contribute significantly to mixed-gas adsorption behavior. A major benefit of this three-regime modeling method is that physically realistic adsorptive selectivities can be adhered to at both extremes of coverage, a property not generally shared by either the IAS or LF models taken singly. This three-regime approach yields better multicomponent equilibria predictions than IAS-only modeling approaches for many relatively nonideal adsorption systems.
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  • 137
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    AIChE Journal 43 (1997), S. 655-664 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Frequency-domain measurements of photon migration were conducted in concentrated polystyrene suspensions to assess their use for on-line particle sizing in undiluted process streams. Using a numerical inverse algorithm, particle-size distributions (PSD) and volume fractions of three latex suspensions with differing distributions were recovered from phase-shift measurements at 15 or less visible wavelengths. Comparison to dynamic light-scattering measurements show excellent agreement. Since it is the propagation characteristics of multiply scattered light instead of the amount of light detected that is employed to solve the inverse problem, the measurement technique provides a self-calibrating (and therefore especially suitable) method for on-line process monitoring of PSD in the chemical-based industries.
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  • 138
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    AIChE Journal 43 (1997), S. 703-714 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The trade-off between model accuracy and computation tractability for model-based control applications is well known. While nonlinear models are needed to capture the detailed behavior of many chemical processes, the resultant structures may not lead to straightforward control implementation. The current work advocates the use of low-order nonlinear models based on wave propagation that are mathematically concise and capture the essential nonlinear behavior of a process. In this work, differential geometry is invoked to achieve input-output linearization of a high-purity distillation column based on a traveling-wave model. A Kalman filter is used to recursively update the parameter values. Comparison with a linear controller based on a two-time constant model shows that the nonlinear controller outperforms the linear controller in tight control of both the overhead and the bottoms composition.
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  • 139
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    AIChE Journal 43 (1997), S. 1108-1113 
    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 storage of natural gas in other light hydrocarbons is one procedure for automotive natural gas usage that reduces the requirement of high-pressure or cryogenic storage. Model solutions of methane in n-butane, propane, and a liquefied-bottled-gas mixture were simulated using the Benedict-Webb-Rubin-Starling equation of state to determine the pressures necessary to maintain a liquid phase with perturbations in both temperature (-1°C to 38°C) and mole fraction (50 to 80 mol% methane). Methane storage in these liquid solutions is between 45 and 93% of an equal “tank” volume of compressed natural gas (CNG) at 21 MPa and 15°C. The simulation results indicate that solutions of this type contain 40 to 67% of the energy of gasoline at pressures that range from 60 to 40% that of CNG at 21 MPa and 15°C.
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  • 140
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    AIChE Journal 43 (1997), S. 1082-1090 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Industrial practice requires immediate and adequate responses to simple questions asked. For example, does a catalyst particle show any tendency to thermal oscillations in the form of a limit cycle? The root to such cycles is found in the eigenvalues of the Jacobian matrix to the reaction rate vector, applying the concept of reaction invariance, a direct consequence of Avogadro's stoichiometric principle for homogeneous stirred tank reactors. However, this concept does not generally apply to heterogeneous reactor dynamics, because it is found in the heterogeneous transports of heat, reactants and products. The transport is an irreversible phenomenon that usually contributes to shifting the eigenvalues to the left and hence increases the stability. Still, effects of transport mechanisms, both internally and externally, on the catalyst particle are important to assess in such industrial analyses. A practical industrial reactor for methanol production was the subject for stability studies, which concluded that thermal oscillations are not likely to occur. During this study, a number of interesting details were examined such as rank deficiency of the reaction matrix and root loci for the temperature dependence of the Jacobian matrix eigenvalues. A practical consequence of eventual thermal cycling of the catalyst particles is a long-term degradation of the catalyst efficiency, as seen in the ammonia synthesis.
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  • 141
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    AIChE Journal 43 (1997), S. 1091-1099 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two reversible reactions are involved in YBa2Cu3O6+x formation: a reaction between BaCO3 and CuO forming BaCuO2 and CO2, and a reaction of BaCuO2 with Y2O3 and CuO forming YBa2Cu3O6 which undergoes phase transformation to YBa2Cu3O6+x upon cooling. In-situ isothermal time resolved HT-XRD of a thin film was used to quantify the effect of CO2 on the kinetics of the first reaction. Increased CO2 partial pressure shifts the reactions to higher temperatures. At high CO2 partial pressure (〉2 vol. %), the rate of the first reaction becomes essentially a step process with a very high activation energy. Noninstantaneous nucleation of the reaction products occurs at low CO2 partial pressure (0.5-1%) and temperatures (700°C). The data fit a 2-D diffusion-controlled mechanism with a zero nucleation rate for BaCO3 decomposition and a second-order nucleation rate for YBa2Cu3O6 formation. A comparison of the kinetics of a thin film (10 mm) as determined by HT-XRD with those of a thick sample (2 mm) determined by TG revealed that the transport of CO2 within the sample pores and to the ambient gas significantly affect the decomposition of BaCO3. For example, the formation of YBa2Cu3O6 in a thick precursor layer occurs in the 840 to 940°C range, exceeding by about 200°C that in which it is formed in thin films.
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  • 142
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    AIChE Journal 43 (1997), S. 1114-1116 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 143
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    AIChE Journal 43 (1997), S. 1153-1162 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The behavior of droplet swarms in liquid-liquid dispersions, especially found in extraction columns, are analyzed by a new fluorescence measurement technique, which represents an extension to the capillary suction method. The measuring principle developd benefits from detectable-emission light intensity of a fluorescent dye even in a trace concentration. The addition of this nontransferring dye to the dispersed phase enables in situ determination of bivariate drop-size/drop-concentration distributions, which provides important information on droplet history for the evaluation of coalescence and breakup rates. Furthermore, the measuring method represents a new approach for the measurment of droplet-size-dependent residence times in extraction columns.
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    AIChE Journal 43 (1997), S. 1300-1308 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Initiaton of incrustation by crystallization mechanisms is studied. An experimental technique was developed by which nucleation of a crystalline phase on a solid surface is investigated at controlled local supersaturation without the interference of particle deposition. Experiments were carried out with different substances and surface materials. The results show that the solid surface may catalyze primary nucleation and hence promote the initiation of incrustation, but this was recorded only at quite high supersaturation. Collision of crystals with the solid surface in a supersaturated solution may initiate incrustation at a reasonably low supersaturation and can be of substantial industrial importance.
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  • 145
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It is now well confirmed that the influence of temperature on the fall-off behavior of dissociation, recombination and chemically-activated reactions can be dramatic. For single-well, single-product dissociation reactions, it is customary to approximate these fall-off surfaces using extensions of Lindemann's empirical expression. We consider here chemical-activation and dissociation reactions possessing multiple wells and multiple products. We show that direct approximation of the rate coefficients via Chebyshev expansions yields reliable and accurate representations of their pressure and temperature dependences, which are superior to those from a Lidemann approach to fit the form factor representing the fall-off surface. The superiority of the method is demonstrated in a study of seven channels corresponding to four different reactions important in combustion chemistry over the ranges 300-3,000 K and 0.02-200 atm.
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  • 146
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    AIChE Journal 43 (1997), 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 velocity of rise and the drag of a single vapor bubble collapsing in another immiscible liquid were measured experimentally. During the process of collapse, the dispersed-phase vapor bubble was transformed to a two-phase bubble with condensate accumulating at the rear of the two-phase bubble and vapor at its top. Such a configuration of a two-phse bubble is commonly known as a drobble. Experimental data for the six pairs of liquids covered a range of drobble (two-phase bubble) Reynolds numbers from 0.003 to 3,000. Two regimes of drobble movement were encountered. In the first regime (Re 〈 100), the drobble maintained its sphericity, and the observed drag was less than the solid-sphere drag predicted by the established solid sphere or Hadamard et al. fluid-sphere drag models. In the second regime, the drobble was deformed and oscillated; the observed drag departed suddenly from predictions of spherical models and increased with increasing Reynolds numbers. The critical Reynolds number covered a range from 100 to 1,000. Empirical models for drobble velocity and drag coefficient are derived.
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    AIChE Journal 43 (1997), S. 2002-2020 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Industrial continuous processes may have a large number of process variables and are usually operated for extended periods at fixed operating points under closed-loop control, yielding process measurements that are autocorrelated, cross-correlated, and collinear. A statistical process monitoring (SPM) method based on multivariate statistics and system theory is introduced to monitor the variability of such processes. The statistical model that describes the in-control variability is based on a canonical-variate (CV) state-space model that is an equivalent representation of a vector autoregressive moving-average time-series model. The CV state variables obtained from the state-space model are linear combinations of the past process measurements that explain the variability of the future measurements the most. Because of this distinctive feature, the CV state variables are regarded as the principal dynamic directions A T2 statistic based on the CV state variables is used for developing an SPM procedure. Simple examples based on simulated data and an experimental application based on a high-temperature short-time milk pasteurization process illustrate advantages of the proposed SPM method.
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    AIChE Journal 43 (1997), S. 2034-2047 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A systematic method is presented for constructing maps of parameter regions with qualitatively different bifurcation diagrams of the reverse-flow reactor (RFR). These maps are most useful for the rational design and periodic operation of an RFR. The method is illustrated by two examples. The map for a single, exothermic first-order reaction contains five regions with qualitatively different bifurcation diagrams when the Damköhler number is the bifurcation variable. The high-temperature branch is isolated in two of these regions. The map for two independent, exothermic first-order reactions contains seven regions with qualitatively different bifurcation diagrams when the adiabatic temperature rise is the bifurcation parameter. Three stable periodic states exist for some values of the bifurcation variable in five of the regions. In some of these regions the intermediate state cannot be obtained upon a slow change in the concentration of the reactants. In all the examples we studied, a stability exchanges of the pseudohomogeneous model occurred only at the limit points of the bifurcation diagrams. An efficient numerical scheme is presented for computing the loci of the singular points of the RFR model.
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  • 149
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    AIChE Journal 43 (1997), S. 2048-2058 
    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 pathways, kinetics and mechanisms underlying the hydrolysis of aliphatic and aromatic nitriles in high-temperature water (HTW) were investigated. The reaction products were the associated amides and carboxylic acids. Autocatalytic kinetics were observed and confirmed by experiment and analysis of the physical chemistry of the HTW reaction environment. A model incorporating two autocatalytic steps captured the observed kinetics well, and the associated optimized rate constants highlighted the key differences in the reaction chemistry of aliphatic and aromatic nitriles. The rate behavior of nitrile hydrolysis at these conditions has tangible consequences regarding optimal processing strategies.
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  • 150
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    AIChE Journal 43 (1997), S. 2059-2072 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Inorganic membrane reactors combine reaction and separation operations in a single unit. Preferential permeation of a product species through the membrane enhances equilibrium-limited reactions beyond the thermodynamic limit. Proper catalyst formulation and spatial distribution also enhance membrane reactor performance. To minimize reactant loss due to high gas permeation, the thickness of the γ-alumina layer in a composite alumina membrane (Membralox) was increased to 17 μm by slip-casting with alumina sol. Among the catalysts investigated a formulation of 1.10 wt. % Pt and 1.36 wt. % Sn supported on γ-alumina pellets yielded the highest activity, selectivity, and stability for the dehydrogenation of ethane to ethylene. Using this catalyst composition, various nonuniform platinum distributions within the pellets were prepared by solution impregnation, while maintaining a uniform distribution of Sn. The effect of nonuniform catalyst distribution on dehydrogenation of ethane in a packed-bed membrane reactor (PBMR) under well-mixed, isothermal conditions was evaluated both experimentally and theoretically. Reactor performance is maximized when the catalyst is concentrated near the surface of the support. Supraequilibrium conversions, about 80% beyond equilibrium values, were obtained with the narrow surface-step catalyst pellets. Experimental results agree well with theoretical predictions, obtained without the use of any adjustable parameters. The effect of membrane thickness on reactor performance was also investigated, by comparing the 17-μm alumina membrane with a 1.2-mm-thick porous Vycor glass, using pellets with the narrow surface-step distribution. For the experimental conditions employed, relatively low permeation through the porous Vycor resulted in conversions near fixed-bed reactor values.
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  • 151
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    AIChE Journal 43 (1997), S. 2123-2132 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Renaturation of protein expressed as inclusion bodies within Escherichia coli is a key step in many bioprocesses. Operating conditions for the refolding step dramatically affect the amount of protein product recoverd, and hence profoundly influence the process economics. The first systematic comparison of refolding conducted in batch, fed-batch and continuous stirred-tank reactors is provided. Refolding is modeled as kinetic competition between first-order refolding (equilibrium reaction) and irreversible aggregation (second-order). Simulations presented allow direct comparison between different flowsheets and refolding schemes using a dimensionless economic objective. As expected from examination of the reaction kinetics, batch operation is the most inefficient mode. For the base process considered, the overall cost of fed-batch and continuous refolding is virtually identical (less than half than of the batch process). Reactor selection and optimization of refolding using overall economics are demonstrated to be vitally important.
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  • 152
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    AIChE Journal 43 (1997), S. 2141-2145 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 153
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    AIChE Journal 43 (1997), S. 2146-2147 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 154
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    AIChE Journal 43 (1997), S. 2148-2152 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 155
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    AIChE Journal 43 (1997) 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 156
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    AIChE Journal 43 (1997), S. 2153-2156 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 157
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    AIChE Journal 43 (1997), S. 2180-2186 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A comprehensive one-dimensional fully coupled hydrodynamic treatment of the film profiles behind liquid slugs in horizontal and inclined gas-liquid slug flow is presented. Experiments were performed in horizontal air-water pipes 32 and 50 mm in diameter, the smaller also being inclined to an angle of 5 degrees. Time traces of film thickness were produced with the use of a wire-probe technique. The experimental results are compared against the theory presented here, as well as previously reported hydrodynamic models. It is concluded that the film profiles calculated by the use of one-dimen-sional models are highly sensitive to the choice of input variables, for example, the slug translational velocity; however, good agreement is achievable provided that consistent hydrodynamic equations and correct input variables are used. It is hoped that the work presented here will influence future mechanistic models of slug flow.
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  • 158
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    AIChE Journal 43 (1997), S. 2194-2202 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The velocity field in a standard mixing reactor with a Rushton impeller is analyzed by using techniques from the theory of nonlinear dynamical systems. It is shown that the dynamical behavior contains a quasi-periodic motion with three frequencies, fp, the frequency associated with the rotation of blades, fp/6, and a third frequency f'. Relying on an evaluation of the correlation dimension equal to 3.9, the phase space is likely to be at least four-dimensional. Moreover, a set of four ordinary differential equations is indeed automatically obtained by using a global vector field reconstruction technique, confirming the existence of a 4-D-deterministic behavior contributing to the dynamics of the system.
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  • 159
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    AIChE Journal 43 (1997), S. 2227-2238 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: During process design of reactive distillation systems, there is often uncertainty in the value of the reaction equilibrium constant (Keq), whether it is determined experimentally or calculated from thermochemical data. The effect of the reaction equilibrium constant on the existence and location of reactive azeotropes (constant boiling reactive mixtures) is explored for chemical equilibrium systems with a single chemical reaction. With a known set of starting points, arc-length continuation was used to track solutions of the equations for reactive azeotropy as a function of the reaction equilibrium constant. The results, portrayed in bifurcation diagrams, reveal that azeotropes may appear or disappear as the equilibrium constant is varied. Results for the esterification of acetic acid with ethanol indicate three distinct regions of phase behavior. The first regime (Keq 〈 0.449) contains a quaternary saddle reactive azeotrope. At intermediate values of the reaction equilibrium constant (0.449 〈 Keq 〈12.5), there are no reactive azeotropes in the system. In the third regime (Keq 〈 12.5), a minimum-boiling quaternary reactive azeotrope appears. In addition, for three reported literature values of the reaction equilibrium constant, each one lies in a different regime. Other examples also illustrate the broad taxonomy of reactive azeotropic systems.
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  • 160
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    AIChE Journal 43 (1997), S. 2239-2245 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The separation performance of binary hydrogen sulfide-hydrogen mixtures by a nanoporous carbon membrane called selective surface flow (SSF) membrane is described. The membrane selectively permeates H2S from H2, and a H2-enriched stream is produced at the feed-gas pressure. A two-stage embodiment of the SSF membrane is described for production of high-purity H2 with high H2 recovery from an equimolar H2S-H2 feed gas. A novel protocol for operation of the two-stage membrane is needed to achieve that separation goal.
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  • 161
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    AIChE Journal 43 (1997), S. 2289-2299 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The competition between heuristic and optimization approaches for process synthesis and process operations problems has caused major controversy in recent years. Heuristics offer fast solutions but no guarantee of optimality. Mathematical programming approaches, on the other hand, offer rigor but suffer from combinatorial explosion of computational requirements. The use of analytical investigations is proposed as a theoretical means to characterize the behavior of heuristics and optimization algorithms and produce a framework that combines the strengths of the two approaches while eliminating their weaknesses. The approach contrasts and complements the current practice in process systems engineering, which is entirely empirical in nature. The proposed paradigm is demonstrated in the context of the multiperiod capacity expansion problem for chemical process networks, a problem having much in common with both process synthesis and operations problems. Analytical investigations for this problem lead to the development of a heuristic that is proved to be asymptotically optimal under standard assumptions about the problem parameters. In the more general context of process synthesis and operations, analytical investigations present a large array of opportunities.
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  • 162
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    AIChE Journal 43 (1997), S. 2903-2910 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To evaluate the effect of viscoelasticity on bubble formation, four rheological parameters of viscoelastic liquids were defined and measured by a rheometer. The effects of operating conditions and concentration of polyacrylamide aqueous solutions (PAA) as viscoelastic liquids on bubble volume and the growth curve were experimentally measured. A high-speed video camera showed that the shapes of a bubble growing in vis-coelastic liquids are not spherical. In this study, a nonspherical bubble formation model was proposed to theoretically estimate the volume, shape and growth curve of bubbles formed from an orifice submerged in viscoelastic liquids which are assumed to follow Maxwell's viscoelastic model. This experimental results in relatively low concentrations of PAA, as well as previous researchers' results, agreed relatively well with the calculated ones by this model.
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  • 163
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    AIChE Journal 43 (1997), S. 2944-2947 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: New correlations, based on the rough hard-sphere theory and an extensive literature database, were developed for the determination of the binary diffusion coefficients of liquid and solid solutes in supercritical solvents. The correlations were tested to predict 107 solute-solvent systems with good results. The input data required for the correlations are the solute molecular weight, temperature, density and the solvent basic properties (molecular weight, critical volume, and critical pressure).
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  • 164
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    AIChE Journal 43 (1997), S. 268-272 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 165
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    AIChE Journal 43 (1997), S. 339-344 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental investigation was conducted to determine the boiling heat-transfer characteristics in a thermosyphon condenser-reboiler of air-separation plants. The test section was a plate-fin heat exchanger of practical size of 0.106 m width and 2.56 m length. The testing fluid was nitrogen. Experiments were carried out within a range of pressure from 150 to 300 kPa, submergence from 1.95 to 2.80 m, and heat flux up to 11 kW/m2 under constant wall-temperature condition. The liquid superheat at the onset of boiling was rather significant. The boiling heat-transfer coefficients obtained agreed well with Chen's correlation modified by Colburn's J factor within a mean deviation of 9.3%.
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  • 166
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    AIChE Journal 43 (1997), S. 363-373 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Batchwise fluidized-bed calcination and sulfation of a limestone were done to investigate particle comminution phenomena and their relation with parallel occurrence of reactions. Operating conditions of the bed were those typical of atmospheric bubbling fluidized-bed combustors. A general framework of comminution phenomena is outlined, which includes different types of fragmentations as well as attrition by abrasion. Comminution processes were characterized by following the modifications of bed sorbent particle-size distribution and the elutriation rates of fines throughout conversion. Mutual interactions between comminution processes and the progress of chemical reactions are assessed.
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  • 167
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    AIChE Journal 43 (1997), S. 1171-1179 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new theoretical approach is proposed for the yield stress of concentrated, flocculated particulate suspensions. Explicit cognizance is taken for the three-dimensional, mechanically rigid particle network held together by interparticle forces wherein the mean coordination number in the assemblage increases and the separation between the particles decreases with an increase in the volume fraction of the solid phase. The Rump-Molerus model relting isotropic normal stress and isotropic normal interparticle force in a bed of single-sized spheres is modified to incorporate the size distribution of particles and extended to the suspension network. The model estimates the yield stress as a function of solids loading for various kinds of size distribution and is in reasonable agreement with experimental data when the surface properties of the particle are held constant.
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  • 168
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The low-temperature oxidation chemistry of linear and branched alkanes is discussed with the aim of unifying their complex behavior in various experimental systems using a single detailed kinetic model. New experimental data, obtained in a pressurized flow reactor, as well as in batch- and jet-stirred reactors, are useful for a better definition of the region of cool flames and negative temperature coefficient (NTC) for pure hydrocarbons from propane up to isooctane. Thermochemical oscillations and the NTC region of the reaction rate of the low-temperature oxidation of n-heptane and isooctane in a jet-stirred flow reactor are reproduced quite well by the model, not only in a qualitative way but in terms of the experimental frequencies and intensities of cool flames. Very good agreement is also observed for fuel conversion and intermediate-species formation. Irrespective of the experimental system, the same critical reaction steps always control these phenomena. The results contribute to the definition of a limited set of fundamental kinetic parameters that should be easily extended to model heavier alkanes.
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  • 169
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    AIChE Journal 43 (1997), S. 1309-1318 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The substitution reaction of hexachlorocyclotriphosphazene, N3P3Cl6, with phenol was performed to synthesize the partially substituted (phenoxy) chlorocyclotriphosphazenes, N3P3Cl6 - i(OC6H5)i, i = 1 - 6 by phase-transfer catalysis (PTC) in an organic phase/alkaline solution. The steric hindrance effect plays a crucial role in this reaction. The reaction system was controlled by both chemical kinetics and mass-transfer effects. The mass transfer of the catalyst between two phases was investigated by a pseudosteady-state liquid-liquid PTC (LLPTC) model. Also, the intrinsic reaction-rate constants of the series substitution and the overall mass-transfer coefficient of the catalyst from the organic phase to the aqueous phase were determined by a combined model. In addition, the corresponding energies, enthalpies, and entropies of activation of the series substitution were also estimated.
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    AIChE Journal 43 (1997), S. 1357-1361 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 171
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    AIChE Journal 43 (1997), S. 1390-1402 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Liquid circulation in bubble columns influences many system properties such as mass transfer and catalyst dispersion. Conditions favorable for liquid circulation often exist only for highly turbulent slurries. Experiments under conditions of lowered surface tension proved conclusively that uniform circulation can exist even in the bubbly-flow regime. Moreover, the measured circulating velocity profile is more plug-shaped in the center core than traditional models, which take a parabolic shape. These observations led to the application of a circulation theory based on an energy-dissipation model for turbulent eddy viscosity, which can be easily computed as a simple function of superficial-gas velocity. Two length scales were used in model calculations depending on flow regime: bubble diameter for bubbly flow and column diameter for churn turbulence. The liquid-velocity profile contained a tuned dimensionless proportionality constant, which resulted in two different average values, k = 2.51 for bubbly flow and 0.0242 for churn turbulence, when tuned to experimental data. The integral average eddy viscosity is numerically equivalent to the eddy dispersion coefficient for bubbly flow. Predicted liquid velocity compared very favorably with new measured values under conditions of low surface tension and with literature values.
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  • 172
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    AIChE Journal 43 (1997), S. 1436-1447 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Droplet breakup in laminar flows is important in emulsification processes and polymer blending. The influence of surfactants on droplet deformation and breakup in a plane hyperbolic flow was studied experimentally in an opposed-stream device. As in the case of simple shear flow, the inhomogeneity of the surfactant distribution along the droplet interface has a pronounced effect. Our results are qualitatively consistent with other numerical studies for droplet breakup in an axisymmetric elongational flow. Also a striking similarity is noted with other experimental observations for the deformation and breakup of polymeric drops in a quasi-steady-plane hyperbolic flow. The critical capillary number for droplet breakup in the experiments correlates with the interfacial viscoelasticity, and a reformulation of the numerical framework in terms of interfacial elasticity parameters is suggested for future numerical work including other linear flows.
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  • 173
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    AIChE Journal 43 (1997), S. 1448-1457 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A revised machine learing methodology is applied to a simulated crystallization process flowsheet for continual imporvement of its performance by generating and analyzing process data. The aim is to identify bands of crucial decision variables leading to zones of best average process performance. The methodology comprises two components: symbolic induction and case-based reasoning. It uses an incremental algorithm to update performance classification rules, which not only improves the efficiency of the symbolic induction of the classification rules by eliminating the need for their periodic reinduction, but also simplifies the case-based reasoning step. The new concepts and procedures are illustrated by application to a potassium nitrate crystallization process comprising a mixed-suspension, mixed-product-removal crystallizer, a hydrocyclone, and a fines dissolver, By identifying and establishing ranges for the most crucial decision variables, namely, feed concentration, flow rate, and cooling stream temperature, three zones leading to an improvement of nearly 12% on nominal average performance are detected within two generations of the classification rules.
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  • 174
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    AIChE Journal 43 (1997), S. 1559-1568 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Thermochemical data of mineral oil fractions are scarce. Due to the complex structure of natural hydrocarbon mixture, standard heat and Gibbs free energy of formation depend on the sample. A procedure for predicting these properties is presented. Both properties depend on the hydrocarbon type and on its molecular weight. The double-bond equivalent (DBE) and the number of olefinic double bounds are the important characterization parameters of the model. DBE can basically be calculated from molecular weight and elemental composition. Alternatively, boiling point and atomic H/C ratio can be used if the model is applied to mineral oil fractions from which boiling curves can be obtained. A criterion for testing the reliability of the estimated DBE value is available, because DBE is also a function of structural group distribution.The relevance of the DBE concept is shown with regard to hydroprocessing of mineral oil fractions. The model can be applied to total average molecules as well as to an arbitrary number of pseudocomponents and continuous mixtures. The difference between feed and product DBE is equivalent to the amount of hydrogen consumed for hydrogenation of unsaturated hydrocarbons. Further properties of the product can be predicted.
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  • 175
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    AIChE Journal 43 (1997), S. 1569-1578 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: For the first time, a model for dynamic adsorption and tension of diffusion-controlled systems has been extended to binary premicellar mixtures of nonionic surfactants of different adsorption capacities and nonideal interactions in the monolayer. Local equilibria between subsurface concentrations and adsorbate densitities are modeled using the nonideal adsorbed solution theory, which describes these two elements. The model shows that larger molecules (those with the smaller adsorption capacity) tend to be preferentially adsorbed at low times, if they have equal adsorption equilibrium constants and diffusivities, and smaller moleules at longer times. This adsorption selectivity is reduced when larger molecules have a much larger adsorption equilibrium constant, or when there are negative deviations from ideality in the monolayer. This model's predictions are compared to tension data for two nonionic surfactants, C12E5 and Triton X-100, at 25°C. The data are represented well by the diffusion-controlled model with a finite diffusion-layer thickness, which describes the faster decrease in tension observed with the bubble surfactometer, compared to data with other techniques. With this model, surface coverages and concentration profiles are calculated, thus elucidating the adsorption selectivity of molecules of different adsorption capacities. Synergistic effect in dynamic tension and adsorption can be predicted. Mild synergism in dynamic tension lowering by the preceding nonionic surfactants is also observed.
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    AIChE Journal 43 (1997), S. 1597-1604 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Hartree-Fock theory and density functional theory were used to compute the enthalpy and entropy changes of dimerization for a number of hydrogen-bonding compounds. In Part 1, the calculational methods and procedures use for the water dimer are described, and the results obtained are compared with those of others and with experimental estimates in the literature. Here, a variety of organic compounds that can self associate and/or cross associate are considered. The results obtained for the self-association of these compounds are compared with estimates obtained from various types of experimental data. The results are also used to examine the validity of group-contribution methods for hydrogen-bonding mixtures and to test a simple estimation procedure for cross dimerization that can reduce the number of calculations, such as those described here, that need to be done.
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  • 177
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    AIChE Journal 43 (1997), S. 1611-1626 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A comprehensive composite database for distillation sieve-tray efficiency is used to develop point efficiency and entrainment correlations based on a model that considers the fluid on the distillation tray to be contained in a liquid-continuous region near the tray deck and a vapor-continuous region on top of the liquid-continuous region. This model allows estimates of the portion of the mass transfer that occurs in each region and the mass-transfer resistance that occurs on the liquid side and vapor side of the interface. For most cases, most of the mass transfer occurs within the liquid-continuous region. The liquid side resistance is often significant.The entrainment correlation is consistent with the work of Bennett et al., which relates entrainment to the ratios of the liquid to vapor density and the froth height to the tray spacing. A simple liquid continuous-only mass-transfer model containing only four empirical parameters correlates the point efficiency data to within 6.4%. Despite a twofold change in vapor Schmidt number, no dependency on vapor Schmidt number is seen. Important dimensionless groupings are the Reynolds number based on the hole velocity, effective froth density, ratio of the liquid inventory to the perforation diameter, and fraction of the tray area perforated. Mathematically simple and accurate methods allow the prediction of the section efficiency for trays operating in cross or parallel flow. They address vapor and liquid mixing, entrainment and a criterion to avoid significant degradation of the tray efficiency due to weeping.
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  • 178
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    AIChE Journal 43 (1997), S. 1641-1648 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 179
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    AIChE Journal 43 (1997), S. 1649-1651 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 180
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    AIChE Journal 43 (1997), S. 1653-1661 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pulsed magnetic field gradient stimulated echo NMR measurements are performed for diffusion and flow of an aqueous phase both within a sample of packed spherical beads and within a 25% porosity Fontainebleau sandstone. The stimulated echo dependence on the gradient pulse area q is used to derive the displacement probability distributions PΔ(X) for fixed observation times Δ. The shape of PΔ(X) as a function of Δ is simulated for computer-generated porous media, and a good agreement is obtained between the experimental NMR data and the simulations.
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  • 181
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    AIChE Journal 43 (1997), S. 1675-1683 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In gas-liquid flows through tee junctions, because of the difference in inertia between the phases, the flowing mass fractions for an individual phase at the outlet sides differ from those at the inlet. This phase separation is an important consideration in delivering fluids and energy through pipe networks in the power and process industry. In this work, air-water and steam-water flows through branching and impacting tee junctions are considered. Under certain conditions (when the volumetric fraction of the liquid drops does not change appreciably and their bulk density is much higher than the gas density, and when the flow rates and/or the gas volumetric fraction are high), these flows can be approximated as irrotational flows of incompressible, inviscid fluids and are amenable to potential flow methods, for example, conformal mapping. For the general case of gas-liquid flows through a branching or impacting tee, a CFD code is utilized to conduct transient flow simulations. Predictions of phase separation for both types of tee junction agree well with experimental data.
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  • 182
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    AIChE Journal 43 (1997), S. 1691-1699 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pore fractal objects are expected to be optimal catalysts, since material is supplied to the narrower pores, which are also shorter through the larger pores where diffusion resistance is smaller. To demonstrate this, diffusion and reaction were simulated on Sierpinski-gasket-type fractal objects and on the corresponding nonfractal uniform-pore structures of the same size, porosity and reactive area. Positive order reactions limited by Knudsen diffusion were shown to exhibit larger rates in fractal than in uniform-pore objects. Fractal catalysts also exhibited a new intermediate domain in which the rate depends only weakly on the kinetics parameters. In nonmonotomic kinetics the branching point (bifurcation point) was extremely sensitive to the pore structure.
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  • 183
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The recovery of the acidic structure and activity during the regeneration step by coke combustion of an HZSM-5 zeolite-based catalyst used in the methanol-to-gasoline (MTG) process in reaction-regeneration cycles was studied. The reactivation kinetics (activity us. coke combustion time) was determined as a function of temperature and time on stream of the reaction step. The validity of the reactivation kinetic model was proven by using it for the simulation of the cyclic operation under conditions of catalyst partial reactivation, together with the kinetic model for the MTG process.
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  • 184
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    AIChE Journal 43 (1997), S. 1529-1544 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Almost-everywhere singular (AES) distributions, usually referred to as multifractal measures, provide an intermediate link between atomic distributions (distributions represented by a countable superposition of Dirac's delta terms) and smooth regular distributions. This article shows how AES distributions can be rigorously treated in connection with distributed-parameter models and presents closed-form expressions and/or recursive, uniformly converging approximation methods for integral transforms (Laplace and Stieltjes). In particular, exact results are obtained and discussed for linear and uniform nonlinear kinetcis and for transport schemes in the presence of continuous mixtures. The physical origin of AES distributions in real systems is also detailed.
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  • 185
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    AIChE Journal 43 (1997), S. 1819-1827 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In a high-temperature catalytic membrane reactor, a plug-flow reactor is combined with a gas-separative membrane. By selectively removing one of the reaction products, the reaction mixture is prevented from reaching equilibrium, and a higher conversion can be obtained. This concept is only valid for reactions that are limited by the thermodynamic equilibrium, such as the direct dehydrogenation of propane to propene. A tubular H2-selective silica membrane was characterized [αH2/C3H8 = 70-90 at 500°C] and used as the gas-separative membrane. The membrane reactor was filled with a chromia/alumina catalyst. The kinetics of the catalyst was studied. At 500°C the deactivation of the catalyst is slow, and the propene yield is almost constant for at least 10 h of operation. Under well-chosen process conditions, the propene yield is at least twice as high as the value obtained at thermodynamic equilibrium in a conventional reactor.
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  • 186
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    AIChE Journal 43 (1997), S. 1849-1860 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model developed for SiO2 deposition in porous Vycor glass using SiCl4 hydrolysis describes reaction, diffusion and evolution of the pore structure due to accumulation of the solid product. The deposition reaction is described by transient heterogeneous kinetics in terms of the concentrations of silanol and chloride groups in the product layer as well as those of the gaseous reactants. For typical deposition conditions the pseudo steady-state approximation for surface species could lead to erroneous predictions. Pore structure evolution is modeled by incorporating results of percolation theory. For this purpose the porous glass is represented by a Bethe lattice with coordination number 3 and alternatively by a decorated Bethe lattice in which each bond is replaced by a composite bond consisting of two bonds in series. The second network can capture the effect of pore radius variation along a single pore. For the decorated lattice, pore connectivity interruption at a higher void fraction leads to thinner deposits and shorter deposition times for pore plugging compared to the corresponding ones for the simple lattice.
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  • 187
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    AIChE Journal 43 (1997), S. 1589-1596 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To reduce the number of adjustable parameters that appear in the thermodynamic modeling of hydrogen-bonding fluids, the use of ab-initio molecular orbital calculations in the form of Hartree-Fock and density functional theories to compute thermodynamic properties are considered. In particular, the enthalpy and entropy changes on hydrogen bonding for water are computed. The theory, the computational methods and the basis sets used, as well as the results for water, are discussed. The results obtained are compared with those of others and with experimental estimates from the literature to determine the validity of the methods that are then used in this extended study. The results obtained here are also used to examine the validity of mixture group contribution results obtained here are also used to examine the validity of mixture group contribution methods for hydrogen-bonding mixtures, to develop simple estimation procedures for model parameters, and to reduce the number of calculations such as those as those described that need to be done.
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  • 188
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    AIChE Journal 43 (1997), S. 1605-1610 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method is presented for a relatively accurate, noniterative, computationally efficient calculation of high-pressure fluid-mixture equations of state, especially targeted to gas turbines and rocket engines. Pressures above 1 bar and temperatures above 100 K are addressed. The method is based on curve fitting an effective reference state relative to departure functions formed using the Peng-Robinson cubic state equation. Fit parameters for H2, O2, N2, propane, methane, n-heptane, and methanol are given.
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  • 189
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    AIChE Journal 43 (1997), S. 1627-1636 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Supercritical water oxidation of isopropyl alcohol was investigated in a pilot-scale reactor. A computational fluid-dynamics model developed reveals the detailed flow field, chemical-component distribution, temperature distribution, and salt-particle trajectories in the reactor flow domain. The near-wall fluid temperature from the numerical analysis was compared with experimental temperature data. The temperature comparison was within a 3% error band. The effect of the chemical kinetic rate was investigated for four different rates. Turbulent salt-particle trajectories were also calculated to investigate the effect of particle sizes on salt deposit on the wall. Also, a method of calculating the adiabatic reaction temperature was developed to estimate reaction temperatures prior to a full numerical simulation.
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  • 190
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    AIChE Journal 43 (1997), S. 1637-1640 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 191
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    AIChE Journal 43 (1997), S. 1727-1736 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The magnitude and direction of the ultrasonic radiation forces that act on individual particles in a standing-wave field were determined using a microscope-based imaging system. The forces are calculated from measured particle velocities assuming that the drag force, given by Stokes' law, is exactly counterbalanced by the imposed ultrasonic forces. The axial primary radiation force was found to vary sinusoidally with axial position and to be proportional to the local acoustic energy density, as predicted by theory. The magnitude of the transverse primary force was determined by two independent methods to be about 100-fold weaker than the axial force. Separation concepts exploiting the transverse force for cell retention have been successful despite the great disparity in magnitude between the axial and transvers-force components. This may be explained by the reduced hydrodynamic forces on aggregated particles in transverse flow due to their alignment in the sound field.
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  • 192
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    AIChE Journal 43 (1997), S. 811-817 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Results from steady and unsteady, two-dimensional simulations of tertiary current distributions at and below the limiting current density are presented. The simulations are based on dilute-solution theory, with coupling of the concentrations of the ionic species through the electrical field. The electrical field is calculated from the electroneutrality constraint. Results confirm and extend previous theoretical predictions of the electricalmigration enhancement of the limiting current. To demonstrate the potential utility of general current-distribution solvers, measured temporal variations of the rate of copper deposition in the presence of an oscillating shear flow are measured and simulated. Experiments agree well with simulations.
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  • 193
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Transvascular and interstitial fluid movements are involved in many important biological processes such as convective macromolecular transport and contribute to the mechanical behavior of tissue. Although intimately coupled, there is a tendency in the literature to regard these two fluid-transport mechanisms separately; if the interaction is considered, the description is usually confined to the local level (e.g., transvascular or interstitial perivascular). A general framework presented here combines transvascular and interstitial fluid movement with the mechanics of soft tissue and integrates macro-and microscopic views of the phenomena. On the macroscopic level, interstitial fluid transport is described by adapting the field equations of the poroelastic theory using average field variables defined on a scale of several blood vessel diameters (∼ 1 mm), while transvascular transport is described by a generalized Starling's law. As an example, the model equations have been specialized for a spherical solid tumor and an analytical solution is presented for the transient redistribution of interstitial fluid following a rapid change in vascular pressure or flow. The model describes the overall average profiles of the interstitial fluid pressure and velocity, as well as the dilatation, displacement and stress of the solid matrix. Moreover, on a smaller length scale the model can describe the local fluid movement (perivascular) using the average field variables as boundary conditions. The basic theory provides new insight into understanding the fluid transport in biological tissues and a valuable tool for determining relevant fluid-transport parameters. Implications for improving drug delivery to solid tumors are also discussed.
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  • 194
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    AIChE Journal 43 (1997), S. 853-869 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Numerous experimental investigations on the vertical transport of dense gas-solid suspensions indicate that particles tend to segregate toward the tube wall. Although models based on the kinetic theory analogy can predict such patterns for perfectly elastic particle-particle collisions, the predictive ability of these models breaks down for inelastic collisions. In the present effort, a mathematical model is developed that incorporates two mechanisms that give rise to the lateral segregation of solids: interactions associated with individual particles based on a kinetic theory treatment and interactions associated with collections of particles based on an analogy with single-phase turbulent flows. Although these two mechanisms have been treated independently by previous workers, their combined contributions to the overall flow behavior have not been thoroughly investigated. The effect of such a treatment on the sensitivity of the model predictions to the inelasticity of particle-particle collisions is explored. A key element in eliminating the undue sensitivity appears to be a consideration of the effects associated with the collective motion of particles on the kinetic theory expressions. The resulting model can predict the expected segregation patterns for systems characterized by inelastic collisions, as well as many of the other salient features of vertical gas-solid flows.
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  • 195
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    AIChE Journal 43 (1997), S. 1921-1922 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 196
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    AIChE Journal 43 (1997), S. 2368-2372 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 197
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    AIChE Journal 43 (1997), S. 2535-2545 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Model predictive control is used extensively to control continuous-process systems. Application of a shrinking horizon model predictive control strategy is used to predict and control the end product quality of composite laminates produced by batch autoclave curing. The main contribution is the demonstration, using a laboratory-scale autoclave, of the feasibility and advantages of a control strategy that adjusts the batch recipe on-line to correct for unmeasured disturbance: entering the process. Readily available, on-line secondary measurements are used in conjunction with the process model to predict (and hence control) quality-related end product properties. On-line monitoring is also used to monitor the process even after the possibility of on-line correction has passed. The results show that this approach significantly reduces end product quality variance.
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  • 198
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    AIChE Journal 43 (1997), S. 2405-2414 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dilute suspensions of neutrally buoyant, uniform-diameter spheres in a viscous liquid are sampled through pores in the wall of a stirred tank. These studies are performed to investigate screening effects near the sampling orifice that cause samples to be deficient in solids. The ratio of sphere concentration in the sample to that of the original suspension ranges from 0.08 to 1.12. Sample concentration decreases with decreasing sampling pore diameter and increasing stirring rates. The objectives of this work are both to obtain experimental relationships and to develop predictive techniques relating flow fields to sample concentration.Sample concentration is predicted by calculating particle trajectories in the region near the pore and by accounting for steric exclusion. Particle trajectories can differ from fluid streamlines due to lift forces generated in the flow field. These estimates constitute a priori predictions, since they do not rely on or introduce any empirical parameters. Predicted values of sample concentrations agree closely with data.
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  • 199
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    AIChE Journal 43 (1997), S. 2432-2445 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The phase holdups and the heat-transfer behavior were studied experimentally in three-phase fluidized beds over a pressure range of 0.1-15.6 MPa. Bubble characteristics in the bed are examined by direct flow visualization. Pressure effects on the bubble coalescence and breakup are analyzed mechanistically. The study indicates that the pressure affects the hydrodynamics and heat-transfer properties of a three-phase fluidized bed significantly. The average bubble size decreases and the bubble-size distribution becomes narrower with an increase in pressure. The bubble-size reduction leads to an increase in the transition gas velocity from the dispersed bubble regime to the coalesced bubble regime, an increase in the gas holdup, and a decrease in the liquid and solids holdups. The pressure effect is insignificant above 6 MPa. The heat-transfer coefficient between an immersed surface and the bed increases to a maximum at pressure 6-8 MPa and then decreases with an increase in pressure at a given gas and liquid flow rate. This variation is attributed to the pressure effects on phase holdups and physical properties of the gas and liquid phases. A mechanistic analysis revealed that the major heat-transfer resistance in high-pressure three-phase fluidized beds resides in a liquid film surrounding the heat-transfer surface. An empirical correlation is proposed to predict the heat-transfer coefficient under high-pressure conditions.
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  • 200
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    AIChE Journal 43 (1997), S. 3223-3231 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The standard industrial process for the purification of natural gas is to remove acid gases, mainly hydrogen sulfide and carbon dioxide, by the absorption and reaction of these gases with alkanolamines, but the lack of reliable and accurate vapor-liquid equilibrium (VLE) data impedes the commercial application of more efficient alkanolamine systems. The objective of this research was to develop an FTIR apparatus and an in-situ technique capable of making VLE measurements of acid-gas-aqueous alkanolamine systems and to improve the accuracy of vapor-liquid equilibrium measurements at low hydrogen sulfide and carbon dioxide concentrations. The new FTIR apparatus and technique were tested in VLE measurements of low concentrations of carbon dioxide and hydrogen sulfide in aqueous mixtures of diethanolamine.
    Additional Material: 15 Ill.
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