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  • Chemical Engineering  (691)
  • 1985-1989  (691)
  • 1950-1954
  • 1988  (691)
  • 101
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 34 (1988), S. 366-382 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A three-dimensional radiation model coupled with two-dimensional mass balances for the intervening chemical species is solved for the photochemical chlorination of ethane. The analysis was carried out using the full mechanistic kinetic sequence and employing polychromatic radiation for a process conducted in a tubular reactor placed inside an elliptical reflector.Theoretical predictions were compared with bench-scale experiments and showed excellent agreement. Using the validated model, computational experiments were conducted to explore the influence of reactor design and operational parameters upon the degree of chlorination. Dichlorination reactions were also added to the kinetic model to analyze reactor behavior from the viewpoint of selectivity. The a priori design method described can be applied from first principles and requires no experimentally adjustable parameters.
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  • 102
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    AIChE Journal 34 (1988), S. 383-388 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Bifurcation problems with slowly varying control parameters are of interest in several research areas, including catalyst deactivation, combustion, and lasers and other nonlinear optical devices. Significant theoretical work has been devoted to the study of these dynamic phenomena, but very little directly relevant experimental information is currently available. Results are presented here from an experimental study of the dynamic behavior of a catalytic reaction system due to a deliberately slowly varied control parameter. Attention is focused on the dynamics due to slow passage through simple limit and Hopf points.
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  • 103
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    AIChE Journal 34 (1988), S. 694-697 
    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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  • 104
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    AIChE Journal 34 (1988), S. 510-513 
    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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  • 105
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    AIChE Journal 34 (1988), S. 524-525 
    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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  • 106
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    AIChE Journal 34 (1988), S. 753-762 
    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 general physical model of a typical batch extraction system employing liquid surfactant membranes is developed. The model takes into account the continuous-phase resistance and the interfacial resistance along with permeation through a composite emulsion globule. It also quantifies the loss in extraction efficiencies by leakage of the encapsulated phase due to membrane breakage. The physical model is easily adapted to apply to the case of transport facilitation wherein the solute is reacted in the internal phase to yield products incapable of permeating through the membrane phase. Experimental data on o-chlorophenol extraction are satisfactorily correlated with the model.
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  • 107
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    AIChE Journal 34 (1988), S. 803-813 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new approach to represent the deviations from ideality of electrolyte solutions is derived on the basis of the assumptions of specific interactions of Brönsted and of local electroneutrality of Chen. The model consists of two contributions due to long-range forces, represented by the Debye-Hückel theory, and to short-range forces, represented by local compositions through nonrandom factors. With only two adjustable parameters per electrolyte, the model is valid for the whole range of electrolyte concentration, from dilute solution up to saturation. Results are compared with those obtained from two-parameter or one-parameter models of Meissner, Bromley, Pitzer, and Chen et al. The model presented in this work consistently produces better results and reproduces the experimental values from the dilute region up to saturation.
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  • 108
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    AIChE Journal 34 (1988), S. 551-557 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Design equations are derived for calculating the properties of an aerosol generated in a tubular flow reactor operated at a constant rate of formation of condensable monomer. These equations lead to a set of characteristic dimensionless groups. Independently, it is shown that nearly monodisperse aerosols can be generated by: (1) separating particle formation and growth processes, (2) operating with a narrow residence time distribution, and (3) minimizing monomer concentration gradients. These criteria can be used in solving the design equations over ranges of the dimensionless groups suitable for monodisperse aerosol production. In general, high rates of monomer formation are desirable, subject to the desired particle size and concentration, but an upper bound may result from coagulation.
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  • 109
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    AIChE Journal 34 (1988), S. 583-601 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: All process designs are subject to uncertainties which make it impossible to state with complete certainty that a design will work. This study presents a measure of design confidence which considers the nature of the uncertainty and the operability of the process as a whole. This measure, called design reliability, quantifies the likelihood that a design will work. Detailed analyses are presented for three special cases: designs subject to random uncertainties, designs subject to fuzzy uncertainties, and designs subject to both random and fuzzy uncertainties. Practical procedures for estimating design reliability in these special cases are also presented.
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  • 110
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    AIChE Journal 34 (1988), S. 679-683 
    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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  • 111
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    AIChE Journal 34 (1988), S. 692-693 
    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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  • 112
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    AIChE Journal 34 (1988) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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  • 113
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    AIChE Journal 34 (1988), S. 743-752 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A prototype of a sodium heat pipe reactor for steam reforming processes has been developed and tested at energy levels up to 6 kW. Both experimental and model simulation data were obtained. Temperature profiles at nonflow and nonreaction flow conditions were used to adjust the parameters of the model, along with an intrinsic rate equation measured in a differential, bench-scale apparatus.Very good agreement between experiment and model was found for approximately 50 runs under steady state reaction conditions covering a range of process variables. Advantages of the heat pipe as a reactor energy source were confirmed. These include isothermal wall temperatures, energy flux transformation, adjusted flux profiles, and rapid startup. These measurements and computations have provided a model from which optimized configurations have been determined.
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  • 114
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    AIChE Journal 34 (1988), S. 672-675 
    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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  • 115
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    AIChE Journal 34 (1988), S. 688-691 
    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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  • 116
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    AIChE Journal 34 (1988), S. 702-703 
    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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  • 117
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    AIChE Journal 34 (1988), S. 733-742 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Monomer partitioning between the aqueous and polymer phases in a latex determines many properties of an emulsion polymerization, such as the reaction rate, molecular weight development and, if operated under refluxing conditions, the reaction temperature. A unique two-chamber vapor-liquid equilibrium cell was used during this investigation to obtain an in situ separation of the aqueous phase from the latex, thus permitting a direct determination of the compositions of the aqueous, polymer, and vapor phases in a latex, even under refluxing conditions. Thermodynamic analysis of the vapor-liquid equilibrium problem allows the prediction of the composition of all phases from measured values of the temperature and pressure only. These predictions agreed well with data from other investigations under nonrefluxing conditions and with the aqueous and vapor phase compositions from this investigation. The polymer phase composition data for vinyl acetate polymers with average molecular weights in excess of 106 showed consistently higher polymer volume fractions than predicted. This latter result may be due to crosslinking or strong entanglements resulting from increased chain branching at these high molecular weights.
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  • 118
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    AIChE Journal 34 (1988), S. 873-876 
    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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  • 119
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    AIChE Journal 34 (1988), S. 912-921 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Manufacture of optical waveguide preforms by modified chemical vapor deposition (MCVD) is theoretically investigated. For the first time, a model accounting for the concurrent heat transfer, chemical kinetics, and silica aerosol dynamics during lightguide preform fabrication by MCVD is presented. Silica particles are formed by high-temperature oxidation of SiCl4, grow by coagulation, and deposit to the preform walls by thermophoresis and Brownian diffusion. Assuming first-order SiCl4 oxidation and approximating the aerosol size distribution by a log normal function throughout the process, five partial differential equations describe this process. The emphasis of this study is on the achievement of high process yield (deposition efficiency of MCVD).Process conditions for operation in the particle transport-limited and reaction-limited regimes are quantitatively identified. Operation in the former regime results in complete oxidation of the inlet SiCl4 but only about half of the product SiO2 particles deposit to the tube wall. Operation in the latter regime results in limited oxidation of inlet SiCl4 (about 40%) but almost all product SiO2 particles deposit to the tube wall. This study shows that high process yields and deposition rate can be achieved in lightguide preform manufacture by MCVD by combining operation in the reaction-limited regime with recycling of the exit gases from the preform tube.
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  • 120
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    AIChE Journal 34 (1988), S. 1119-1127 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This work follows the global input/output linearization approach for the design of control systems for nonlinear plants of Kravaris and Chung. A robust nonlinear state feedback is proposed for uncertainties considered as a class of bounded perturbations to the state model. A Liapunov-based approach is used to guarantee uniform ultimate boundedness.
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  • 121
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    AIChE Journal 34 (1988), S. 1157-1163 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The understanding of the mechanism of wall-to-bed heat and mass transfer in liquid-fluidized beds requires knowledge of the effect of the motion of individual particles on transfer processes. Experimental studies on the enhancement in mass transfer due to motion of a particle in the proximity of the transfer surface are presented. Mathematical relations based on a mechanistic model are obtained to describe the variation of the enhanced rate with time. The model parameters are correlated in terms of the particle Reynolds number, the wall-to-particle distance, and an interaction parameter that accounts for the background fluid motion. The results of this work would be of use in modeling transfer processes in other liquid-solid systems.
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  • 122
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    AIChE Journal 34 (1988), S. 1190-1199 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The absorption of mixtures of nitrogen oxides into aqueous solutions of NaOH in the range of partial pressures of 0.004- to 0.05-atm NO and 0.002- to 0.015-atm NO2 was investigated. Absorption experiments were conducted in a gas-liquid contactor that permitted independent variation of the gas and liquid mass transfer coefficients. The results were analyzed in terms of a model which accounted for diffusion, reaction, and formation of higher oxides and oxyacids in the gas and in the liquid phases. Absorption of both HNO2 and N2O3, formed in the bulk gas and within the gas diffusion film, were found to be significant. Using a rate coefficient of 8.8 × 10-3 mol/s · cm3 · atm3 for the formation of HNO2 in the gas phase (England and Corcoran, 1975), a value of the absorption factor, H √Dk, for N2O3 of 2.5 × 10-3 mol/s cm2 atm was determined at 25°C. This value was found to decrease with temperature and was 1.2 × 10-3 at 40°C. The use of concentrated base as an absorbent solution prevented the formation of nitric acid mist, a problem encountered in many previous studies of NOx absorption.
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  • 123
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    AIChE Journal 34 (1988) 
    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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  • 124
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    AIChE Journal 34 (1988), S. 1086-1093 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Reaction mechanism and rates were determined from 803 to 1,073 K for the carbochlorination of Al2O3 and of Al, Si and Fe-mixed oxides using Cl2 and C slurried in a stirred melt of NaCl - AlCl3. Alumina chlorination rates of 0.33-2.0 × 10-8 kmol/s were obtained using C:melt weight ratios between 1:21 and 1:42. The reaction rate was proportional to C loading at temperatures below 923 K, while gas-liquid mass transfer was rate-controlling at higher temperatures. Carbochlorination of the combined oxides in coal fly ash at 923 K and oxide conversions less than about 50% was also gas-liquid mass-transfer-controlled. At higher conversions, dissolution became the rate-controlling factor. A 40% (molar) AlCl3 melt was more effective than a 48% AlCl3 melt for the selective chlorination of Al2O3 over SiO2.
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  • 125
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    AIChE Journal 34 (1988), S. 1128-1134 
    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 rate of dissolution of sphalerite is shown to be directly proportional to the concentration of substitutional iron impurity in the solid. This is attributed to the formation of a narrow impurity band within the forbidden band gap of the sphalerite. The impurity band is of iron d-orbital origin. The transfer of electrons between this d-orbital band and the oxidant is energetically more favorable than the transfer of electrons between the valence band and the oxidant. A fundamental model combining the electronic structure of sphalerite and semiconductor electrochemistry is presented. An equation is derived that describes the rate of dissolution as being first order for the concentration of iron in the solid and half-order for the concentration of the oxidant. This is in agreement with the experimental evidence.
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  • 126
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    AIChE Journal 34 (1988), S. 1321-1331 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Gross error identification in dynamic processes is important in ensuring proper process control. This paper describes the application of a generalized likelihood ratio (GLR) method for identifying gross errors caused by biases in measuring instruments and controllers, process leaks, and failure of controllers. As shown in the application to steady state processes (Narasimhan and Mah, 1987), this method provides a general framework for identifying different types of gross errors whose effect on the process can be modeled. An important feature of the work is the treatment of closed-loop dynamic processes. The formulation of the hypotheses of the GLR method proposed by Willsky and Jones (1974) is extended for this purpose. For estimating the time of occurrence of the gross error, a simple chi-square test on the innovations (measurement residuals) is used, which is computationally more efficient than the method used by Willsky and Jones. Through simulation studies of a level control process the appropriate selection of parameters of the GLR method is investigated.
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  • 127
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    AIChE Journal 34 (1988), S. 1367-1372 
    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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  • 128
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    AIChE Journal 34 (1988), S. 1381-1383 
    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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  • 129
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    AIChE Journal 34 (1988), S. 1395-1397 
    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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  • 130
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    AIChE Journal 34 (1988), S. 1027-1030 
    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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  • 131
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  • 132
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  • 133
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    AIChE Journal 34 (1988), S. 1550-1558 
    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 optimal control policy for the maximization of the secreted heterologous protein in a fed-batch bioreactor was obtained using SEY2102 as a model host yeast and SUC2-s2 as a model secretory protein. A dynamic model for host cell growth, gene expression, and the secretion of expressed polypeptides was formulated. The optimal system trajectory contains multiple singular arcs that are distinct from one another. Optimal control requires transitions between these singular arcs. Optimal transitions between multiple singular arcs with bounded controls are uniquely located in observance with the Minimum Principle of Pontryagin. An iterative numerical search strategy for determining the optimal control showed successful convergence properties.
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    AIChE Journal 34 (1988), S. 1539-1549 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Heat transfer analysis of falling film evaporation on a bank of horizontal tubes is investigated in this study. Liquid falling from one tube to the next lower one is considered as a thin liquid jet impinging on the top of the tube with a uniform free falling velocity. The hydrodynamic and thermal solutions are obtained by a finite difference method. In these solutions the heat transfer coefficients are modified to account for waviness.Liquid film thickness and local and average heat transfer coefficients are obtained for the constant heat flux and isothermal boundary conditions. Convective heat transfer effects are shown to be dominant as Peclet number increases. Heat transfer coefficients for the tubes in a tube bank decrease from the first tube onwards until the fully developed region is reached. The present predictions agree favorably with the reported heat transfer data.
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  • 135
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    AIChE Journal 34 (1988), S. 1486-1492 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Theoretical and experimental studies of pressure swing adsorption (PSA) cycles for various extents of purging have been conducted. In both the theoretical and experimental portions, pressurization was accomplished with product rather than with feed. A simple, local equilibrium model was employed, and the results were analyzed by the method of characteristics. It was found that for difficult separations (i.e., closely spaced isotherms and/or heavily contaminated feeds), incomplete purging, e.g., as little as 50% complete, yielded recoveries attainable only at much higher pressure ratios with complete purge. Conversely, for easy separations (i.e., widely spaced isotherms and dilutely contaminated feeds), incomplete purging was less attractive, yielding only slight improvement over complete purge.Splitting oxygen from air with zeolite 5A is moderately difficult due to the proximity of the isotherms and due to the predominance of the more strongly adsorbed nitrogen in the feed. This case was also modeled and was studied experimentally. The experiments yielded nearly double the recovery of oxygen for minimal purge compared with that available with complete purge. The productivity of oxygen was relatively high, e.g., 0.0378 m3(O2 at STP)/kg (adsorbent) · h. Those experiments validated the trends predicted theoretically.
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    AIChE Journal 34 (1988), S. 1528-1538 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Monte Carlo simulations of sintering and redispersion of supported metal catalysts, based on an atomic migration mechanism, are presented. The support surface was modeled as a square grid with metal atoms located at various grid points. Interaction energies between metal atoms, and between metal atoms and support sites were specified. The probability of movement of each metal atom during one time increment (iteration) was calculated from the interaction energies. The effects of interaction energies, metal loading and initial distribution of the metal were examined. The model predictions are in good qualitative agreement with experimental observations. The model predicts “apparent” movement, splitting and coalescence of entire metal particles; these experimentally observed phenomena have usually been cited as evidence that sintering occurs by a particle migration mechanism.
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  • 137
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    AIChE Journal 34 (1988), S. 1563-1567 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1581-1583 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1663-1672 
    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 sudden reduction in the feed temperature of a packed-bed reactor may lead to a transient temperature rise, referred to as a wrong-way behavior. As expected, the axial dispersion of heat decreases the magnitude of the temperature excursion and prolongs the transient shift to a new steady state. In addition, the thermal dispersion may enable the wrong-way behavior to ignite a low-temperature steady state leading to a disastrous runaway of the reactor. Moreover, it may create a transient high-temperature wave, which moves initially in the upstream direction. The axial dispersion of heat can lead to some behavioral features which are qualitatively different from those of a model which ignores it. The transient temperature excursion does not exceed a value, which can be estimated by a simple analytical expression.
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    AIChE Journal 34 (1988), S. 1709-1712 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1722-1725 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1740-1742 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1757-1759 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 34 (1988), S. 1781-1788 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Electrolyzing sparingly soluble gases as they are absorbed from bubbles can be significantly facilitated by addition of a soluble redox couple which serves to increase both mass and charge transfer rates. A diffusion layer model is used to calculate reaction-catalyzed mass transfer rates in regions of boundary layer penetration by reactive bubbles for the case of (m, n)-order irreversible homogeneous reaction. The dissolved redox catalyst is continuously regenerated at the solid electrode surface. Approximate solutions, which relate surface flux to concentration driving force, are in excellent agreement with the numerical solutions under conditions of fast homogeneous reaction and concentrated catalyst (modified Damköhler number and dimensionless catalyst concentration greater than 3). Diffusion layer thickness is calculated from the mass transfer coefficient kp in penetrated regions. A model based on spherical penetrating bubbles is used to determine kp and specific surface area ap of penetrated regions from kpap values that have been measured in gas-liquid flow through a packed bed. The mass transfer behavior provides useful insight into why the penetration process is so effective in increasing overall reaction rates.
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    AIChE Journal 34 (1988), S. 1821-1832 
    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 population balance for batch aggregation of particulate suspensions is recast in a form that may be solved simply and accurately. The transformed equation is deduced with the introduction of only one additional parameter, which is found to be a constant for all cases. The transformed equation is tested by comparison with some analytical solutions with which it is found to be in excellent agreement. In particular, the equation is shown to predict correctly the rate of change of total particle number and volume. Compatible descriptions of linear growth and nucleation are developed with similar success.The method is then applied to modeling the in vitro growth and aggregation of kidney stones (calcium oxalate monohydrate crystals). It is found that these phenomena are well described by McCabe's ΔL law, a size-independent coalescence kernel, and first-order kinetics. Simulated particle size distributions and their moments are in excellent agreement with the experimental results.
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    AIChE Journal 34 (1988), S. 1903-1906 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 34 (1988), S. 1913-1915 
    ISSN: 0001-1541
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    AIChE Journal 34 (1988), S. 2083-2087 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 34 (1988), S. 1417-1422 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A novel microreactor with a rapid direct quench system was developed to study fast hydrocarbon pyrolysis reactions. Heating of reactants inside the reactor was achieved by a Curie Point Pyrolyser. The propane pyrolysis reaction was studied at four different temperature levels: 600, 700, 800 and 900 °C. Pyrolysis times were varied from 0 to 2 s between 600 to 800°C and from 0 to 1 s at 900°C. The primary reaction products were methane, ethylene, hydrogen and propylene. Using a developed and very effective quench technique increased the production of olefins and reduced the formation of methane. A first-order kinetic analysis performed on the experimental data between 600 and 700°C yielded an activation energy of 216 kJ/mol, which is in the range of other researchers.
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    AIChE Journal 34 (1988), S. 1732-1735 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1743-1746 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 34 (1988), S. 1752-1756 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 34 (1988), S. 397-402 
    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 ideal adsorbed solution (IAS) theory of adsorption of gas mixtures is extended to the case of energetic heterogeneity. A heterogeneous ideal adsorbed solution (HIAS) behaves ideally on a particular site, but energetic heterogeneity causes a segregation in the composition of the adsorbed phase. Equilibrium properties are obtained by integrating over a multivariate energy distribution based upon perfect positive correlation of site energies. The fact that predictions from HIAS are always an improvement over IAS indicates that heterogeneity is a factor that must be considered in theories of mixed-gas adsorption. Errors in HIAS predictions may be caused by steric exclusion of the larger molecules from micropores accessible to smaller molecules.
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    AIChE Journal 34 (1988), S. 426-434 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effect of pore structure on the gasification of two chars impregnated with potassium carbonate catalyst is investigated. Well-characterized char samples were reacted with carbon dioxide, water vapor, and oxygen. The effects of catalyst on the magnitude of the gasification rate as well as on the entire rate vs. conversion pattern are reported. Reactivity and structural data are analyzed to obtain a meaningful comparison of the gasification behavior for all char-gas pairs. Initial intraparticle catalyst dispersion was strongly influenced by the pore structure of the chars. During gasification with carbon dioxide and water, the catalyst appeared to redistribute itself in accordance to the accepted reaction mechanism, leading to superior catalytic activity. The reported measurements indicate that both the pore structure of the chars and the chemistry of a particular reaction are key factors in determining the overall catalytic performance.
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    AIChE Journal 34 (1988), S. 465-473 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model is developed to calculate the impedance response of a semiconductor electrode to a sinusoidal current perturbation. The model accounts explicitly for electron and hole transport as well as generation and recombination through band-to-band mechanisms and through bulk interband electron acceptors of specified energy. The resistive (real) component of the impedance is shown to be sensitive to the concentration, distribution, and energy level of the bulk sites. The capacitive (imaginary) component, while useful for determining the dopant level and the flat-band potential of the semiconductor, is relatively insensitive to low concentrations of bulk sites.
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    AIChE Journal 34 (1988), S. 17-24 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Reaction schemes for the thermal cracking of paraffins, naphthenes, olefins, and aromatics, and the associated rate equations, are generated by an algorithm based upon Boolean relation matrices. In order to reduce calculation times for the heavier components, a self-learning system is introduced. This self-learning system avoids repetition of identical calculations by recognizing intermediate species, for which the reaction schemes have already been generated. The software includes routines for standardizing the representation of the species, an information retrieval system, and libraries containing the necessary information for recognition of the species and the reaction schemes for these species.
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    AIChE Journal 34 (1988), S. 525-525 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 34 (1988), S. 541-550 
    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 the reconciliation of measurements of flows and concentrations so that they conform to conservation laws and other constraints, any gross errors in the measurements must be identified in order that they can be either corrected or deleted.A new method is derived for the recursive prediction of the changes in the objective function, and of the statistical tests for the measurements, which would result from the deletion of suspect measurements. Inverses of large matrices are not required and the reconciliation can also be easily calculated for any set of deletions. It is shown that the decrease in the objective function caused by deletion of a single measurement equals the square of the corresponding maximum power measurement statistic, calculated prior to that deletion. An algorithm for the detection of suspect sets of gross errors, whose deletion leads to acceptable values of all statistical tests and process flow rates, is proposed and illustrated.
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    AIChE Journal 34 (1988), S. 567-573 
    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 study was carried out of the momentum and the heat transfer to fine alumina particles injected into a DC plasma jet. Measurements are reported of particle number flux distribution, particle velocity, and inflight particle surface temperature under different operating conditions. The results show that the particle trajectories and associated particle flux distribution depends to a large extent on the particle injection velocity. The maximum particle velocity and surface temperature are noted, however, to remain close to the centerline of the jet, independent of the particle injection conditions. The maximum surface temperature reached by the particles increases with increasing plasma power and the use of an Ar/H2 plasma gas (17 vol. % H2) compared to that for a pure argon plasma.The particle velocity data are in good agreement with the predictions of a two-dimensional mathermatical model used for the calculation of the particle trajectories and temperature history. The model predictions, however, agreed only in trend with the measured particle surface temperatures. Deviations between the two could still be observed at large distances from the point of injection of the powder. The computed particle number flux distributions were narrower than the measured profiles, which can be attributed to the fact that the model did not include, at this stage, turbulent particle diffusion effects.
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    AIChE Journal 34 (1988), S. 618-625 
    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 study of the efficiencies of two plate distillation columns is reported. One column had three rectangular trays with a flow path length of about 1 m, the other was a modified glass Oldershaw column with one tray of 38 mm dia. Tray efficiencies were measured in both columns and point efficiencies were deduced for the rectangular column.The systems studied were ternary and quaternary mixtures of alcohols and water. The results showed that for thermodynamically nonideal systems significant differences existed among the individual component point efficiencies. In the case of an ideal system the component point efficiencies were effectively equal, but tray efficiencies were different due to differing volatilities and composition profiles across the large trays.This study illustrates the need to allow for the above effects in large-column designs for multicomponent systems. The possibility of using laboratory-scale point efficiencies in these designs is explored.
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    AIChE Journal 34 (1988), S. 456-464 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: When thin films of liquid are produced by roll coaters it is commonly observed that the liquid film is not uniform but shows either regular or irregular patterns resulting from hydrodynamic origins. The appearance of the liquid film has been considered to be governed by the flow geometry and dynamics in a nip region between two adjacent solid planes.Experimental work was done to observe the flow geometries in the nip region and patterns of liquid film by using a roll-stationary, transparent flat plate system. Two fundamental mechanisms for rib disappearance in practical high-speed coatings were recognized. It was also found that the constant rib interval for infinite capillary number depends not only upon the minimum gap size but also upon the physical properties of the liquid. Experimental data are presented in dimensionless form for meniscus position, rib interval, constant rib interval, and for the critical or transient conditions of rib formation, rib disappearance, unstead ribbing, and centrifugal splash.Comparison of present results for the speed ratio U2/U1 = 0 with previous results for U2/U1 = 1 shows the significance of the speed ratio to the meniscus position and the rib interval.
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    AIChE Journal 34 (1988), S. 493-498 
    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 analytical, theoretical investigation of mass transfer in a Newtonian, isothermal falling film displaying periodic, finite-amplitude waves is presented. The solution derived provides full information on the mass transfer rate as expressed exclusively in terms of physical properties of the liquid and the completely determined flow.
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    AIChE Journal 34 (1988), S. 229-238 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Theories of batch sedimentation, taking into account the compression zone effect, are reinterpreted and modified. According to the discussion presented and the experimental results shown, characteristics - which are the loci of points representative of layers with the same settling rate and the same solids concentration in the settling zone - rise tangentially to the sediment curve on a height vs. time plot. Mathematical expressions that relate the solids concentration to the variations of the pulp-supernatant interface height and of the sediment height are presented. In addition, the model presented is proposed for use when it is not possible to measure the sediment height. A procedure for calculating the concentration at the top of the sediment is also indicated.Calcium carbonate suspensions in water were selected for testing the equations deduced. The relation between the continuous thickener unit area and the underflow solids concentration was obtained from the batch tests, and is compared with that calculated by the graphic methods of Talmadge and Fitch, and Fitch.
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    AIChE Journal 34 (1988), S. 272-282 
    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 transient behavior of polymer properties following a step change in feed conditions during copolymerization in a continuous-flow stirred-tank reactor has been investigated by both modeling and experiment. For kinetics appropriate to Ziegler catalyzed olefin polymerization, the dynamic response of polymer molecular weight and composition is predicted to be relatively slow; four to six reactor turnovers could be required to reach steady state. In addition, response time depends on the direction and magnitude of change and is generally shorter when a property value is decreased. These model predictions were confirmed by measurement of the transient response of copolymer composition and molecular weight for ethylene-propylene-ethylidene norbornene terpolymerization.The model equations also were used to simulate reactor startups, and it was found that steady state following a startup can be reached in about three reactor turnovers. The initial absence of polymer in the reactor causes the dynamic response to be faster for a startup than for reactor control.
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    AIChE Journal 34 (1988), S. 610-617 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental study was made of tracer dispersion in bidisperse sintered glass materials prepared from mixtures of two sizes of beads with mean diameters of 325 and 95 μm. The equivalent dispersion coefficient increases by a factor of 30 when the porosity decreases from 30 to 12%; this variation is similar to that measured in monodisperse samples. The variation of dispersion can be characterized by the ratio R = ℓd/L1 where ℓd is a length scale deduced from the equivalent dispersion coefficient and L1 is obtained from conductivity and permeability measurements. It is shown that the increase of ℓd/L1 correlates with the loss of porosity during the sintering process. Lightly sintered samples with a percentage of small beads around the minimum of porosity display a nearly Gaussian behavior, with a dispersion coefficient close to that obtained in homogeneous equivalent mixtures. This result is in contrast with very large anomalies observed by other authors. These results imply that dispersion in consolidated samples is sensitive to large-scale inhomogeneities of the materials rather than to their detailed structure.
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    AIChE Journal 34 (1988), S. 658-668 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A model is presented for the supercritical reaction-extraction of a solid component from a bed of porous particles through which the solvent flows. Accounted for are reaction at an intraparticle position, pore diffusion, interphase mass and heat transfer, and flow in a differential reactor. The behavior of the bed is dynamic since both temperature and concentration of extractable solid vary with time.The model is compared with experimental data for the extraction with toluene of kerogen from a bed of Colorado shale particles. Curves of effluent bitumen concentration vs. time were measured and fitted with predicted curves to evaluate three parameters: preexponential factor and activation energy for the conversion of insoluble kerogen to soluble bitumen, and the diffusivity of toluene at the critical point. The predicted curves agreed well with the experimental results and gave reasonable values for the parameters. Rates of reaction-extraction as well as extraction curves exhibited a sharp dip as the reactor was heated through the critical temperature.
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    AIChE Journal 34 (1988), S. 349-349 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 34 (1988), S. 403-410 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Advancing and colliding flow fronts are important fluid mechanical problems in injection mold filling. These are small-scale, transient free-surface flows with a significant impact on the molecular orientation of molded parts. This paper describes a numerical technique for the simulation of transient free-surface flows. The algorithm combines a Galerkin/finite-element discretization of the governing equations with a predictor-corrector scheme for integration in time, and determines simultaneously the flow field and the free surface at every time step. The method is applied to the start-up of a fluid flow initially at rest and impingement of two flow fronts to form a weldline. Comparison of simulation with available experiments on the start-up problem shows very good agreement. Numerical tracking of fluid elements clarifies various aspects of flow-induced deformation of the material.
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    AIChE Journal 34 (1988), S. 980-995 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In this study the impact of the transport processes and the degree of wetting on the overall selectivity of a single catalytic pellet is examined for the commercially important consecutive-parallel network A(g) + vBB(l) → vR1R(l), A(g) + vR2R(l) → P(l). The one-dimensional formulation applies to catalysts in which the active component is concentrated in a thin porous surface shell coating an impermeable support. Model modifications provide an approximate description of uniformly active catalysts. The kinetics are assumed to be first and zero order with respect to the volatile (A) and nonvolatile (B, R) components, respectively, as encountered in many olefin hydrogenations. The common literature assumption of volatile reactant limiting reactions is relaxed by accounting for nonvolatile reactant depletion. The depletion can significantly reduce the desired product (R) selectivity below its intrinsic value attained under fully wetted, no-depletion conditions. A model employing the single limiting reactant assumption cannot predict such selectivity variations. The selectivity is shown to be a complex function of the wetting efficiency, the stoichiometry, and the interacting reactions and mass transport processes. In many cases the intrinsic selectivity is attained for wetting efficiencies exceeding a critical value. Increases in the wetting above this value can reduce significantly the production rate of R because of resistance to A supply through the liquid film. Thus, an optimal range of wetting efficiencies exists for which the selectivity is equal to its intrinsic value and overall rates are high. The significance of the main findings with regard to trickle-bed reactor performance are discussed.
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    AIChE Journal 34 (1988), S. 1030-1030 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 34 (1988), S. 1043-1047 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 763-780 
    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 preliminary synthesis of ordinary distillation schemes for separating a single feed into desired products is examined. Nonsharp products are emphasized, i.e., when components are desired in more than one product. Such sets lead naturally to columns with incomplete separation of the key components, including one-section columns. Stream bypassing around separators and limited stream splitting are permitted. Sequences cannot have separators with identical key components, and only limited product fragmentation is considered. A heuristic ordering of separation options, coupled with a depth-first application on a pictorial or a matrix representation of a stream, is proposed. Subsequently a best-first search identifies the few better schemes. Partial sequences are (sub)optimized heuristically. Employing the present methodology on an example problem of four components and products resulted in annual cost savings of 42%, compared to the best sequence isolating the feed components.
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    AIChE Journal 34 (1988), S. 814-824 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mixtures of water, oil, and surfactant often form microemulsions where tiny drops of oil (or water) are dispersed in a matrix of water (or oil). A microemulsion is a partially-ordered fluid in which the surfactant molecules exist in an oriented layer at the boundary between the continuous phase and the discontinuous phase. This work proposes a molecular-thermodynamic model that is useful for calculating a variety of phase diagrams observed in microemulsion-forming systems.The model is based on a revised form of Widom's abstract representation of a microemulsion; that representation provides a procedure for calculating essential contributions to the configurational entropy. In Widom's representation, all molecules are difunctional dumbbells such that all the hydrophilic ends are situated together in some lattice sites and all the lipophilic ends are situated together in other sites. A form of Guggenheim's quasichemical theory is used to evaluate the combinatorial contributions that correspond to Widom's picture. Chemical association of surfactant molecules and physical interactions are also taken into account. Minimization of the Gibbs energy yields a distribution function for representing micelle sizes.Calculated ternary phase diagrams are in good agreement with experimental results. Different types of diagrams can be obtained upon changing physically significant model parameters. A study of how these parameters affect phase behavior provides insight on microemulsion stability.
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    AIChE Journal 34 (1988), S. 1146-1156 
    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 performance of the industrial HCN synthesis Andrussow reactor on a Pt gauze catalyst is simulated using rate equations for 13 simultaneous unimolecular and bimolecular surface reactions. Individual rates have been determined experimentally for reactants, intermediates, and products on polycrystalline Pt, and the model therefore contains no adjustable parameters except for reactant flux limits. Predicted selectivities of HCN formation agree quite well with those observed in commercial reactors, and a distinct optimum with feed composition is obtained near that observed experimentally. In addition, behaviors are predicted at compositions, pressures, and temperatures inaccessible to the commercial reactors. Both isothermal and nonisothermal situations are examined. Questions concerning the validity of models, reactant flux limits, and the decoupling of simultaneous surface reactions are considered.
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    AIChE Journal 34 (1988), S. 932-937 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mixing time and power consumption have been measured in baffled, paddle-agitated cylindrical tanks with single- and double-impellers, and mixing efficiency has been defined by a reciprocal of the product of the mixing time and power consumption. The mixing efficiency and mixing time of double-impeller agitation have been compared with those of single-impeller agitation, and they have been related, through a circulation time, to the flow patterns obtained from the measurements of mean axial and radial velocities.
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    AIChE Journal 34 (1988), S. 955-963 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Modern equation-oriented simulators solve systems of equations and procedures using Newton's method or its variants. Partial derivatives of the output variables of procedures with respect to their input variables are required and are usually approximated by perturbation or quasi-Newton methods. Here it is shown how this partial derivative information can be computed exactly for procedures in general, with particular applications to flash and multicomponent distillation procedures. Results indicate that 1. physical property procedures should provide analytical derivatives of properties in addition to point values; 2. commonly used procedures for vapor-liquid equilibria calculation can easily be modified, and should be, to also return output/input gradients; and 3. the use of exact derivatives at all levels results in significant improvements in efficiency over present methods.
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    AIChE Journal 34 (1988), S. 1006-1019 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Scaling rules for both linear and nonlinear elution chromatography with independent solutes are discussed. The scaling method utilizes smaller diameter particles with high mass transfer rates. The column length, diameter, and cycle time are then scaled so that pressure drop, separation, and throughput are the same or better than in the old design. The new design uses much less packing and cycles more rapidly than the old design. Mathematical derivation shows that the scaling rules for systems with linear and nonlinear isotherms are the same in certain circumstances. Gaussian solutions are used for studying linear systems. Mass transfer zone and diffusive wave analyses are used for constant and proportional patterns, respectively, to describe elution when plateaus form at the feed concentration. Numerical examination of the constant-pattern elution curve using the Thomas solution shows that the scaling rules are applicable to short columns, which means that there is a negligible entrance effect on the scaling rules. The Thomas solution also shows that the mass transfer resistance has little effect on the scaling rules for the proportional-pattern wave of a nonlinear solute. Shock and diffusive wave analyses based on the local equilibrium model are employed to describe the separation when the elution curves do not have plateaus. The calculated results show that the scaling rules are followed exactly when pore diffusion controls. Separation of two noninteracting nonlinear components and of a linear and a nonlinear component remains constant when these scaling rules are followed. Several example calculations are used to demonstrate the method.
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    AIChE Journal 34 (1988), S. 1031-1033 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1048-1050 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 781-789 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experimental measurements are reported of oil-water flows in a 20 cm ID pipe at mean velocities between 2.7 and 35 cm/s, at deviation angles θ from vertical between 0 and 65°, and at water flow rate fractions between 30 and 100%. The distribution of the water volume fraction αw across a pipe section is obtained using local high-frequency probes. The mean water volume fraction in the section and the slip velocity Vs between oil and water are also determined. High Vs values (up to 50 cm/s) are measured at large deviation angles; they are associated with oil droplet swarms or continuous oil phase zones. Both αw profiles and Vs values depend only on the mean water volume fraction and not on the total flow rate Qt in the range investigated. At low oil volume fractions αo, all droplets are concentrated close to the upper side of the pipe. At larger αo values, a slower linear variation of αw with the distance y from the axis is measured. A model is suggested relating the slope ∂αw/∂y in a vertical plane to the existence of internal density waves in the stratified mixture.
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    AIChE Journal 34 (1988), S. 1332-1340 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Critical impeller speed for the suspension of solid particles, Ncs, has been measured in 0.3, 0.4, 0.57, 1.0, and 1.5 m ID mechanically agitated contactors. Tap water and quartz particles (100, 340, 700, 850, 2,000 μm) were used as liquid and solid phase, respectively. The impeller speed was varied from 3.5 to 13.3 r/s and solid loading from 0 to 50 wt. %. Three types of impellers were employed: disk turbine, pitched turbine downflow, and pitched turbine upflow. The impeller diameter to vessel diameter ratio was varied in the range 0.175 to 0.58 and the impeller blade width to impeller diameter ratio was varied in the range 0.25 to 0.4. The impeller clearance from the tank bottom was varied from 0.5 to 0.167 of tank diameter. The effect of impeller blade thickness was also studied.The pitched-blade impellers were found to be more efficient than a conventional disk turbine, and the pitched turbine downflow type was found to be more efficient than a pitched turbine upflow impeller. An attempt has been made to explain the mechanism of suspension on a rational basis and a correlation has been proposed for the estimation of Ncs that is expected to be useful in design.
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    AIChE Journal 34 (1988), S. 1354-1360 
    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 carbon dioxide was studied as a solvent for the enzymatic oxidation of cholesterol with molecular oxygen. Enzymes isolated from Streptomyces sp., Norcardia sp., Pseudomonas sp., and Gloeocysticum chrysocreas are active in supercritical carbon dioxide.For the oxidation of cholesterol to cholest-4-ene-3-one (via cholesterol oxidase) from Gloeocysticum chrysocreas, turnovers are almost two orders of magnitude higher than those found in aqueous solutions; initial rates of the reaction catalyzed by Streptomyces sp. in supercritical carbon dioxide are comparable to or greater than those found in aqueous solutions. Cholesterol oxidase from Gloeocysticum chrysocreas is stable in supercritical carbon dioxide at 100 bar and 35°C, while the enzyme from Streptomyces sp. is not. A trace amount of water is necessary for catalysis in carbon dioxide.The rate of oxidation is increased markedly by addition of small amounts of tert-butanol and iso-butanol, moderately by ethanol, slightly by acetone and n-butanol, and not at all by addition of methanol. Solubility data cannot explain these observations.EPR spectroscopy reveals no large conformational changes in the enzyme from Gloeocysticum chrysocreas as a function of carbon dioxide pressure or cosolvent addition. However, EPR spectroscopy indicates that aggregation of cholesterol molecules in supercritical carbon dioxide is strongly affected by changes in pressure or cosolvent content. The degree of cholesterol aggregation correlates well with observed rate enhancements.
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    AIChE Journal 34 (1988), S. 1034-1038 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1398-1402 
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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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    AIChE Journal 34 (1988), S. 1221-1224 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1233-1248 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1275-1286 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Isoactive-solvent (ISAC) theory is a thermodynamic framework for the case where the components of a solution exist in different pure states: liquid solvent and gaseous solutes (absorption of gases); solid solvent and liquid solutes (sorption of liquids); and liquid solvent and solid solutes (solubility of mixed electrolytes). Properties of mixed solutes are predicted from known activities of single solutes by assuming that solute-solute (but not solute-solvent) molecular interactions are ideal. Equations for an ISAC ideal solution are exact in the limiting case of a solution of identical solutes. The thermodynamic potential is a Legendre transformation of the Gibbs free energy: Ψ = G - μ1n1, where the solvent is component number 1. The ISAC standard state is the real single-solute mixture.
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    AIChE Journal 34 (1988), S. 1164-1184 
    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 continuum model for multicomponent distillation in the minimum reflux limit, first proposed by Nandakumar and Andres, is refined for the special case of constant relative volatility (CRV) and constant molar overflow (CMO) and is extended to columns with multiple feeds and multiple products. A relaxation algorithm for calculating steady-state conditins in any minimum reflux CRV, CMO column is established. This generalization of Underwood's classic treatment of single-feed columns is used to explore the characteristics of several single-feed and multiple-feed distillation systems. Critical operating points at which the steady-state composition profile in a minimum reflux column is indeterminate are identified and analytical expressions predicting the location of these points are established.
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    AIChE Journal 34 (1988), S. 1215-1220 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988) 
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    AIChE Journal 34 (1988), S. 1267-1274 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Several oil-water mixtures were contacted by air in a sieve tray distillation column simulator. The oil was mineral spirits with 183-206°C boiling range and 51.8° API gravity. Two sieve tray designs were used, and both hydraulic and mass transfer measurements were made, the latter utilizing acetone as the transferring solute. It was found that gas agitation caused the mixtures to behave as a homogeneous liquid that followed general correlations for pressure drop, liquid holdup, froth height, downcomer liquid level, and fractional entrainment. No unusual problems with foaming or entrainment were observed. Mass transfer efficiency was influenced by oil-water ratio, with mild minima occurring at about 50 vol % mixtures. It was concluded that, when the immiscible liquids are both present in significant proportions, designers need not avoid formation of a second liquid phase for fear of unusual hydraulic or mass transfer behavior.
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    AIChE Journal 34 (1988), S. 1310-1320 
    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 light-scattering techniques have been applied to study the kinetics of droplet evaporation and attendant interfacial phenomena. The first technique, which is particularly useful for noisy data, utilizes the fast Fourier transform of phase function data (intensity vs. scattering angle) to obtain the size by comparing the phase function with Lorenz-Mie theory. The second method applies optical resonance measurements to obtain very precise measurements of size and/or refractive index as functions of time. The techniques have been used to measure the slow evaporation of multicomponent and single-component organic microdroplets, rapid evaporation of water droplets, and rapid evaporation of droplets of aqueous solutions and surfactant solutions. The experiments were performed in an electrodynamic balance, which was used to suspend single microdroplets in a polarized laser beam. Rapid evaporation rate data yield information on the surface temperature, and data for surfactant solution evaporation show that insoluble monolayer formation at the microdroplet surface reduces the evaporation rate by a factor of 200. In addition, it is shown that droplet explosion due to surface charge effects can occur well below the Rayleigh limit of charge.
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    AIChE Journal 34 (1988), S. 1361-1366 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1376-1380 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1392-1394 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1455-1467 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mathematical models are developed to examine two alternative means of boron doping from boron-rich glass films. For the planar source diffusion system, in which boron diffusion and glass film growth occur simultaneously at high temperature (900-1,200°C), glass film growth rates and the degree of doping achieved are predicted. In most cases, the solubility limit of boron in silicon is attained at the silicon surface. It is found that depletion of the boron source wafers used in this process may be slowed considerably by their removal from the reactor after a short time. Model predictions for an alternative method, in which the glass film is pregrown at low temperature (300°C) and the diffusion subsequently performed at high temperature, demonstrate a strong dependence of the boron surface concentration on the initial boron content in the pregrown glass film, for concentrations of boron near the solubility limit. The conditions for which a masking film of SiO2 is insufficient to prevent boron diffusion into silicon, known as mask failure, are also predicted by the models.
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    AIChE Journal 34 (1988), S. 1573-1576 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 34 (1988), S. 1585-1594 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Aqueous polymer-polymer two-phase systems provide a powerful method for separating biomolecules by extraction. When a complex mixture of biomolecules (e.g., a fermentation broth or a solution of lysed cells) is added to such a system, biomolecules partition uniquely between the two phases, achieving separation.A thermodynamic framework is presented for optimizing extraction performance in biological separations. First, a molecular-thermodynamic model, based on the osmotic virial equation, is proposed to describe phase equilibria for dilute aqueous mixtures containing polymers and protein. Second, experimental phase-equilibrium data (protein partition coefficients) are reported for a number of model proteins including albumin, lysozyme, and α-chymotrypsin. To interpret and correlate the experimental data, Low-Angle Laser-Light Scattering (LALLS) measurements were made to determine osmotic second virial coefficients for aqueous mixtures containing polymers, proteins, salts (KCl, KH2PO4 and K2SO4 at concentrations of 50 and 100 mM) and several combinations of polymer-polymer and polymer-protein pairs. Combined with electrochemical measurements (differences in potential between the two phases and protein net charge), these data provide parameters for the model to calculate the desired phase equilibria. A comparison of calculated and experimental results indicates that the virial-equation model provides good prediction of binodals and a reliable basis for estimating infinite-dilution protein partition coefficients for biotechnical process design.
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    AIChE Journal 34 (1988), S. 1627-1633 
    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 numerical computation is carried out to study the interaction of rotation and natural convection inside a finite horizontal cylinder. The natural convection is due to differential heating on the two ends, while the rotation is along the axis of the horizontal cylinder. The aspect ratio, length of the cylinder to its radius, is 2.0. The Grashof number is fixed at 1.43 × 106 with air as a working fluid. The effect of rotation is examined with Gr/Re2 from 7.0 × 10-2 to ∞, which covers the range from rotation dominated flow to buoyancy dominated flow. It is found that when rotational speed is relatively small or Gr/Re2 » 1, the effect of rotation is to render the spatial heat flux distribution more uniform. As the rotational speed increases, the heat transfer rate distribution on the end surfaces is more homogenous and its level is also reduced. When the rotational speed is sufficiently high (Gr/Re2 « 1.0), heat transfer is by conduction only and the whole fluid inside the enclosure rotates as a rigid body. It is shown that there exists a rotation speed range in which one can have both relatively high and uniform heat transfer rates on the end walls.
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