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  • Life and Medical Sciences  (2,476)
  • Inorganic Chemistry  (1,169)
  • Chemical Engineering  (1,167)
  • 1995-1999  (4,812)
  • 1950-1954
  • 1996  (1,668)
  • 1995  (3,144)
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  • 1995-1999  (4,812)
  • 1950-1954
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  • 101
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 713-726 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Protein partitioning kinetics was measured for the semibatch extraction of lysozyme in a laboratory-scale, liquid-liquid spray column. The organic, isooctane phase contained reverse micelles formed from the anionic surfactant, sodium di-2-ethylhexyl sulfosuccinate. For the extraction of protein from aqueous to reverse micellar phases, experiments were performed over a range of dispersed-phase flow rates for cases of the organic- or aqueous-phase dispersion. The influence of aqueous-phase pH and ionic strength, which influence electrostatic interactions between protein and reverse micelles, was also investigated. Results were interpreted in terms of a two-film model of mass transfer. The nature of the dispersed pahse could significantly influence the partitioning kinetics, while study of the droplet hydrodynamics suggested that stagnant drops were formed regardless of which phase was dispersed. Literature correlations for describing the droplet-formation process and droplet hydrodynamics predicted measured values satisfactorily. Attempts wer also made to predict overall mass-transfer coefficients based on existing correlations describing mass transfer during droplet formation, free rise (or fall), and coalescene. Predicted values of KL were 2-10 times greater than measured values, probably because of large concentrations of surfactant used to formulate the reverse micelle phases. This approach did, however, provide detailed information on the quantity of protein transferred during the successive processes of droplet formation, free rise (or fall) and coalescence.
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  • 102
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 727-741 
    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 discretization procedure for the agglomeration equation is presented. The intrinsic problems caused by discretization of the particle-size distribution are mitigated by using proper probability functions. Thus, the new discretized equation predicts the same total number of particles as its continuous counterpart and guarantees conservation of mass. This general method can correctly predict any two properties simultaneously and is not limited to number and mass. Simulation results with various agglomeration kernels show that the new method provides significant improvements over the conventional discretization method. Furthermore, the new method allows the user to choose equal-size intervals or geometric-size intervals with any geometric ratio to cover the particle-size range. In addition to flexibility, the latter feature leads to better accuracy in particle-size distribution predictions.
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  • 103
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 753-766 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new methodology for gage control of sheet and film processes is presented. A linear process model is developed that is capable of describing many of the interesting features of the process, including a noisy and moving gage sensor, significant process noise, strong coupling between the gage in different lanes, constraints on the actuators, and significant time delay between the actuators and the sensor. An automatic control of this process given this model form is designed. Novel features of the controller are that it can contend with information from a moving sensor and handle hard constraints on the actuators. Control performance and robustness to noise are demonstrated favorably via simulations.
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  • 104
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 742-752 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: With the growing environmental concern, it is necessary to improve process simulation and develop design tools to account for environmental factors in the synthesis of large-scale chemical processes. A major obstacle in tackling this problem is uncertainties in some of the technical and economic parameters, which lead to uncertainties in design, plant performance, and cost estimates. Further, a conceptual process design involves the identification of an optimal flowsheet structure from many alternatives stituting the “superstructure.” Synthesis and optimization of large-scale processes involving uncertainties often require considerable computational effort. A novel algorithm presented here is based on simulated annealing for the process synthesis of large-scale flowsheets having several configurations and considers uncertainties in the process design systematically. This new “stochastic annealing algorithm,” provides an efficient approach to stochastic synthesis problems by incorporating a penalty term in the objective function and balances the trade-off between accuracy and efficiency based on the annealing temperature. It has been used to study a benchmark synthesis problem in the HDA process. Savings of up to 80% in CPU time has been achieved without significant loss of solution precision with stochastic annealing, compared to simulated annealing with a fixed sample size. It can be applied to analyze efficiently any complex process flowsheet and provide valuable insights into process feasibility based on optimal design, plant performance, and uncertainty issues.
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  • 105
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 777-790 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Most advanced control applications rely on good dynamic process models. The performance of the control system depends on the accuracy of the model used. Typically, such models are developed by conducting off-line identification experiments on the process. These identification experiments often result in input-output data with small output signal-to-noise ratio, and using these data results in inaccurate model parameter estimates. Prefilters are used to separate useful information from the noise in the input-output data and to improve parameter estimates. A systematic design procedure for selecting a prefilter using discrete wavelet transforms is presented. The design procedure provides explicit information on the compromises in prefilter design, interpreted in terms of parameter variance and bias. The prefilter design procedure is then applied to identify a second-order output error model.
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  • 106
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 767-776 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Identification of low-order linear multiinput/multiouput models can lead to accurate descriptions of the dynamic behavior of a continuous crystallization process. While open-loop experiments exhibit an oscillating crystal size distribution, improved experimental conditions can be established through stabilization of the process with a simple single-loop feedback controller. The resulting closed-loop identification problem is studied using low-order linear multivariable input-output models. Two closed-loop identification methods are applied, one of which was recently introduced to provide accurate approximate models in general closed-loop process configurations. Identification and validation data are obtained from an evaporative pilot crystallizer, and the identified models are validated in terms of time- and frequency-domain responses. A fourth-order, three-input three-output model is shown to describe accurately the process dynamics. The results are compared with a linearized and reduced first-principles model.
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  • 107
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 232-238 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dissolution and crystal growth on the (010) cleavage surface of mineral gypsum have been studied by scanning force microscopy, which allows observation of surfaces while they are in contact with aqueous solutions. Etch pits formed on the (010) surface in contact with solutions undersaturated with respect to gypsum are oriented in relation to the [001] zone axis. Edges parallel to [001] are stable or move only slowly. Edges parallel to [100] and [101] move more rapidly. Crystal growth by migration of step edges is observed in contact with supersaturated solutions. The inhibition of crystal growth by phosphonate produces gross changes in the texture of steps and terraces.
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  • 108
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    AIChE Journal 42 (1996), S. 214-231 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The long-time behavior of a reaction mixture containing infinitely many species in isothermal continuous stirred tank reactors (CSTRs) is analyzed and contrasted with that in a plug-flow reactor (PFR). The reaction kinetics considered are irreversible first-order, irreversible coupled pseudo first-order, and reversible first-order. Asymptotic lumped kinetics for the mixture as a whole are developed as a function of feed properties and reactor type. Such lumped kinetics in many cases are of the power law form, with the exponent for a CSTR being lower than that for a PFR. Conditions under which non-power-law kinetics arise are given. Due to the wide spread of reactor residence times, the mixture in CSTRs admits a much richer variety of asymptotic possibilities than in the PFR. The results uncover some behavioral differences and relationships between CSTRs and a PFR for converting complex mixtures such as petroleum distillates or coal liquids.
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  • 109
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    AIChE Journal 42 (1996), S. 271-276 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 110
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    AIChE Journal 42 (1996), S. 901-909 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A process-engineering model is presented for the stratified-wavy-to-intermittent (SW-I) flow-pattern transition in slightly inclined gas-liquid pipe flow. The main parameter for predicting (in) stability of wavy flow in inclined pipes is the average liquid holdup, which was found to reach a maximum, critical value at flow-pattern transition. Observed values of the critical liquid holdup vary between 0.07 and 0.42, depending on pipe diameter, angle of inclination and transport properties of the gas-liquid system. Measurements were performed in transparent glass pipes of 26- and 51-mm dia., at ten angles of inclination (0.1° ≤ β ≤ 6.0°), using air/water and air/tetradecane (n-C14H30) systems at atmospheric pressure. Flow-pattern maps are presented for selected angles of inclination, showing excellent agreement between predicted and observed flow-pattern boundaries.
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  • 111
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    AIChE Journal 42 (1996), S. 921-926 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Random walks are used to examine dispersion between miscible fluids in one-dimensional, prefractal porous medium. Mixing in such media is anomalous and several nonlocal theories have been proposed to describe this non-Fickian characteristic. This work simulates dispersion via a random walk in a prefractal media by incorporation local and spatially nonlocal effects and compares the results with laboratory experiments. Results suggest that nonlocal models fit experimental data better than local models.
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  • 112
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    AIChE Journal 42 (1996), S. 927-931 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The sedimentation velocity of multiparticle suspensions was investigated experimentally for cases where the column wall is likely to have a nonnegligible effect. The experiments demonstrate that the container wall diameter influeces the falling velocity only for dilute systems, which is in contrast with a widely used, established empirical relationship.
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  • 113
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    AIChE Journal 42 (1996), S. 940-952 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It has been shown that small-amplitude oscillations can augment the diffusional flux across a cylindrical tube by several orders of magnitude through Taylor-Aris dispersion phenomena (Aris, 1960). This enhancement in mass transport is selective for species with different molecular diffusion coefficients. This article shows that by coupling fluid oscillations with a reversible absorption in a stationary phase, the transport of species, which have similar molecular diffusivities but different affinities for the stationary phase, can be enhanced selectively. We developed analytical and asymptotic solutions to the enhancement of mass transfer as a result of the interaction between reversible absorption and fluid oscillations in a cylindrical tube. These results were qualitatively confirmed by experiments with a model system. For purely oscillatory flow, the maximum selectivity (the ratio of the fluxes of the species to be separated) achievable is 4.4 for solute species with widely different affinities for the stationary phase. The superposition of a small-amplitude steady backflow, however, can greatly increase the selectivity, but at the expense of throughput. Analysis shows that this technique may offer improvements relative to conventional liquid membrane separations, if the solute affinities for the stationary phase do not greatly differ or if a thick membrane is required for stability.
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  • 114
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    AIChE Journal 42 (1996), S. 932-939 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The volumetric flow rate of liquid and gas through small gigaporous particles was measured by a new method that isolates single particles in a test apparatus. To our knowledge, this is the first direct confirmation of flow through gigaporous particles made at pressure drops experienced during normal operation. High-performance liquid chromatography particles from 30 to 50 μm in diameter, previously reported to exhibit convection-enhanced intraparticle mass transfer, were studied. Using a CFD model of the test system, the permeability of individual particles was determined from the pressure-drop-flow-rate relationship. The average measured permeability of the particles studied is 7.89 × 10-15 m2 with no dependence on particle size. This is 4 to 17 times greater than values calculated from models currently used to estimate the permeability of these kinds of particles. No other experimentally measured values of permeability have been reported for particles of this size. The results of this study might imply that the intraparticle structure does not behave like a bed of uniformly packed microspheres, but rather as an inhomogeneous assemblage of microparticles. The measured permeability values offer the possibility of developing better models of the intraparticle flow field under normal operating conditions. Knowledge of the intraparticle flow field is an important step in deriving predictive models of convective mass transfer in these types of particles.
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  • 115
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    AIChE Journal 42 (1996), S. 953-959 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The formation of a filter cake during mechanical dewatering (filtration and expression) of sludge is studied using one-dimensional nuclear magnetic resonance (NMR) imaging of porosity profiles. The experiments clearly showed the formation of a porosity gradient during filtration and the disappearing of this gradient during expression, forming a cake with a uniform porosity. This technique makes it possible to investigate the material behavior of the porous medium, which is needed before any model calculations can be performed. The results indicate that NMR imaging is useful in nondestructive monitoring of the filtration and expression process of sludge.
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  • 116
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    AIChE Journal 42 (1996), S. 960-972 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Sedimentation and consolidation of suspensions of fine particles were analyzed by integrating experimental measurement of properties in a centrifuge with a comprehensive numerical model. The yield stress and settling velocity for tailings from tar sands extraction were determined experimentally as a function of the volume fraction of solids. The evaluated state functions were used to simulate batch settling and consolidation, and the results compare well with long-term settling tube tests. This approach is very attractive where gravity sedimentation may take many years, and it allows prediction of the rate of clear water production, total time for sedimentation and consolidation, and the maximum concentration of solids.Scaling of the sedimentation between centrifuge and field conditions is discussed. Conversion of permeability-void ratio relationships from geotechnical experiments to state functions of hindered settling velocity is demonstrated, allowing the use of data derived from a variety of experimental techniques.
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  • 117
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    AIChE Journal 42 (1996), S. 383-390 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Multiple diffusion reactions are frequently encountered in the modeling of heterogeneous catalytic reactors. Obtaining an accurate estimate of the yield and selectivity in such reactions is crucial for an optimal design of reactors. Due to the inadequacy of analytical techniques in handling nonuniform catalyst shapes and mixed boundary conditions, numerical techniques are often employed to compute these design parameters. Among other numerical techniques, the boundary element method (BEM) is a superior method to solve linear diffusion reaction problems. The integral nature of the BEM formulation allows for boundary-only discretization of the particle, thus reducing the computer execution time and the data preparation effort. A boundary element algorithm is developed to solve a network of linear diffusion reactions in porous catalyst particles in two dimensions. For this purpose, a matrix of fundamental solutions is defined and derived. The developed algorithm is applied to complex reaction networks to obtain the yield of intermediates for nonregular catalyst shapes and nonuniform boundary conditions. The method can be used as a design tool to study particle scale modeling in detail and can be incorporated into an overall reactor model.
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  • 118
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    AIChE Journal 42 (1996), S. 405-408 
    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 range of small, medium and large pore zeolite, and their modified forms are studied for their ability to separate di- from monobranched isomers of hexane. The separation studies are carried out using high-temperature (250-350°C) gas chromatography. Beta(H,Ba) is found to be the most effective separator of 2,3-dimethylbutane and 3-methyl-pentane and is therefore studied for its sorption capacities toward the two hexane isomers.
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  • 119
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    AIChE Journal 42 (1996), S. 1010-1032 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A generalized modeling framework for process synthesis alternatives is proposed, based on fundamental mass/heat-transfer principles. A multipurpose mass/heat-transfer module is introduced as the building block of the framework, whereas basic block-superstructure rules (such as splitting, mixing, and bypassing) are used to develop a systematic representation of process units and process structures, conventional or not. Process synthesis procedures are explored within this modeling framework, where synthesis alternatives are not postulated as process unit networks, but explored simultaneously without predefining synthesis schemes, as combinations of mass/heat-exchange stream matches. The representation potential of this framework is illustrated with examples from unit operations, whereas synthesis example problems are presented to show the broad range of process alternatives that can be modeled, identified, and optimized.
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  • 120
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    AIChE Journal 42 (1996), S. 409-421 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A novel gas purification technique called rapid pressure swing absorption (RAPSAB) was developed by integrating the best features of membrane contacting, gas-liquid absorption, and pressure swing adsorption (PSA). In this cyclic separation process, a well-packed microporous hydrophobic hollow-fiber module was used to achieve nondispersive gas absorption from a high-pressure feed gas into a stationary absorbent liquid on the module shell side during a certain part of the cycle followed by desorption of absorbed gases from the liquid in the rest of the cycle. The total cycle time varies between 20 s and upwards. Separation of mixtures of N2 and CO2 (around 10%) where CO2 is the impurity to be removed was studied using absorbent liquids such as pure water and a 19.5% aqueous solution of diethanolamine (DEA). Three RAPSAB cycles studied differ in the absorption part. Virtually pure N2 streams were obtained with DEA as absorbent demonstrating the capability of bulk separation to very high levels of purification. Numerical models developed predict the extent of purification for pure water and the DEA solution for one of the simpler cycles. Model simulations describe the observed behavior well.
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  • 121
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    AIChE Journal 42 (1996), S. 431-439 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The crystallization of phenanthrene from toluene with carbon dioxide as the antisolvent gas is described. In the GAS process, a pressurized gas is dissolved into a liquid solvent, where it causes a volumetric expansion and lowers the solubility of the solute. Theoretical models are presented for the liquid-phase expansion and the solubility as a function of pressure and temperature. The Nývlt theory for batch crystallization is adapted to predict the pressure profile in the crystallizer needed to maintain a constant supersaturation and growth rate. Generation of seeds is accomplished via a pressure pulse at the saturation pressure. The average particle size of the phenanthrene could be varied from 160 to 540 μm. Creation of seeds doubles the particle size and reduces the coefficient of variation significantly. The residual amount of toluene in the crystals without treatment is approximately 70 ppm. The particles are agglomerates of phenanthrene crystals.
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  • 122
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    AIChE Journal 42 (1996), S. 440-454 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The high throughput and operating cost of the reactor provide the economic incentive in considering the on-line optimization of the LDPE tubular reactor. For an on-line optimization procedure it is crucial to develop a flexible and adaptive on-line parameter estimator, which based on the appropriate measurements from the reactor will adjust certain key model parameters so that the model can capture the actual reactor operation and reliably be used for the real-time optimization of the reactor performance. Various issues involved in developing the on-line estimator for such applications as the mathematical modeling of the reactor, the selection of the adjustable model parameters and reactor measurements, the decomposition of the problem according to the characteristic time constants of various disturbances, and the efficient and robust solution of the mathematical problem are discussed. The tools developed were successfully used on an EXXON high-pressure LDPE tubular reactor. Results from the numerical experiments that are compared with scaled data from a real reactor show that the estimated temperature profiles agree remarkably with those observed at various phases of the reactor operation.
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  • 123
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    AIChE Journal 42 (1996), S. 455-465 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two issues involving the methodology used for on-line control of product quality in batch manufacturing processes are addressed: the generation of fast, data-driven process models and the use of such process models for on-line feedback control of product quality. The methodology is investigated using the example of the control of dispersity and molecular weight distribution in a batch reactor for emulsion polymerization of vinyl acetate. An artifical neural network (ANN) is used as a model to predict the quality as a function of the manipulated variables and on-line measurements. This model is constructed using an augmented dataset that integrates experimental information and knowledge from a mathematical model. The proposed model is compared with other types such as a theoretical model whose key parameters are fitted to experimental data. The hybrid ANN is superior to the parameter-fitting approach for this case. Experimental and simulation studies confirm the advantage of using the proposed model and the predictive control algorithm.
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  • 124
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    AIChE Journal 42 (1996), S. 466-476 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Suppressing the influence of external disturbances on a process is the most common objective of a controller in a chemical plant. A control system that can keep the controlled variables at or near their set point and the manipulated variables lower than their prespecified maximum bounds in the face of load disturbances is wanted. A method is presented to design controllers with disturbance rejection specifications and limits over the control energy. This methodology is based on a special strategy to shape the structured singular value of a closed-loop transfer function matrix.
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  • 125
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    AIChE Journal 42 (1996), S. 477-492 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Effective utilization of measured process data requires efficient techniques for their compact storage and retrieval, as well as for extracting information on the process operation. Techniques for the on-line compression of process data were developed based on their contribution in time and in frequency using the theory of wavelets. Existing techniques for compression via wavelets and wavelet packets are inconvenient for on-line compression and are best suited for stationary signals. These methods were extended to the on-line decomposition and compression of nonstationary signals via time-varying wavelet packets. Various criteria for the selection of the best time-varying wavelet packet coefficients are derived. Explicit relationships among the compression ratio, local and global errors of approximation, and features in the signal were derived and used for efficient compression. Extensive case studies on industrial data demonstrate the superior performance of wavelet-based techniques as compared to existing piecewise linear techniques.
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  • 126
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    AIChE Journal 42 (1996), S. 493-502 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Neural-network-based control schemes are generally designed by replacing standard elements of the classic control schemes by feedforward neural networks. The introduction of discrete time recurrent networks, which are inherently dynamic systems, into those schemes can simplify the design of neural controllers. The concept of applying recurrent networks in indirect adaptive control schemes is described. A combined network cluster consisting of the control network and the model network is constructed to allow the use of the real-time recurrent learning algorithm. To demonstrate the feasibility of the method two simulation examples are presented.
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    AIChE Journal 42 (1996), S. 503-515 
    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 safeguarding methodology of chemical plants is usually based on controlling the instantaneous values of process state variables within a certain operating window, the process being brought to shutdown when operating constraints are exceeded. This method does not necessarily prevent chemical reactors suffering from a runaway during dynamic operations because (a) excessive amounts of unreacted chemicals can still accumulate in the process, and (b) no means are provided to the operating personnel to identify hazardous process deviations. A model-based startup and safeguarding procedure is developed for an industrial adiabatic tubular reactor to improve process safety during startup. The trajectories of manipulated variables are calculated by minimizing the amount of one of the main reactants in the reactor effuent. It is concluded that proper control of the initial reactor temperature profile is critical for a safe startup while the impact of other manipulated variables is relatively smaller than that of the initial reactor temperature profile.
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    AIChE Journal 42 (1996), S. 516-523 
    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 one-sided single-pellet dynamic technique introduced in this article is shown to be a very effective and simple method for the analysis of adsorption and diffusion in porous solids. Moment expressions are presented for reversible and irreversible adsorption processes. Since the adsorption equilibrium constant is the only unknown parameter in the first moment expression, this parameter can be evaluated from a single set of pulse-response experiments. This technique to evaluate the adsorption equilibrium constant is illustrated using ethylbromide as tracer. It is also shown that for a very strongly adsorbing tracer, such as 1,2-dichloroethane in soil, modified moment expressions derived with a semiinfinite boundary condition are necessary unless a criterion developed in this work is satisfied.
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    AIChE Journal 42 (1996), S. 524-531 
    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 effect of high levels of coke deposit on catalyst properties and mass transport through the pores space was studied using commercial catalysts, Pt-Al2O3 and Ni-Mo-Al2O3. Changes in porosity, pore-size distribution and internal surface area of several aged catalysts were compared to those of fresh catalyst. Effective diffusivity was also measured by pulse chromatography. For Pt-Al2O3, which shows a high initial porosity (0.93) and a relative high mean pore radius (300 Å), catalyst properties remain unchanged while coke content increased. For the Ni-Mo-Al2O3 catalyst (with initial porosity of 0.53 and mean pore radius of 50 Å), however, with an increase of 15% in coke content, isolated void regions appear, and porosity, internal surface area and effective diffusivity decrease sharply. Pore and stochastic models were used to interpret the effective diffusivity experimentally measured. A structural parameter in each case, tortuosity factor in pore models, and coordination number in the percolation model were calculated. When coke produces significant changes in catalyst morphology, the tortuosity factor almost doubles its initial value for a coke content of 20%. On the contrary, the percolation model seems to predict changes accurately in porosity, mass trasport coefficient, and an isolated prosity growing from the coordination number matched for a fresh catalyst.
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    AIChE Journal 42 (1996), S. 1195-1195 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 42 (1996), S. 1191-1194 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 42 (1996), S. 1195-1195 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 42 (1996), S. 1197-1198 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 42 (1996), S. 1195-1197 
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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 42 (1996), S. 1198-1199 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 42 (1996), S. 1200-1200 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 42 (1996), S. 1201-1212 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Atomization experiments, motivated by the need to suppress misting of machining oils, were conducted on dilute solutions of polyisobutylene (PIB) in mineral oil using a coaxial air blast atomizer and an optical (Fraunhofer diffraction) particle sizer. Polymer concentrations (0.1 to 1.0 kg/m3) and molecular weight (1.0 to 2.2 million) were varied to determine their effects on aerosol drop-size distributions. The pure oil and PIB - oil solutions were atomized at air/liquid mass ratios near 10 and atomizing air velocities of 150-270 m/s, producing droplet-size distributions with mass mean diameters (MMD) in the range of 7-15 μm for the pure oil. Under identical atomization conditions, the MMDs of PIB solutions were 20-200% higher than pure oil. These observed increases in MMD correspond to significant reductions in the fraction of droplets falling below 5 μm in diameter that constitute the misting problem in industrial machining applications. Observed effects of PIB on atomization are ascribed to the viscoelastic properties of PIB - oil solutions as characterized by the elongational viscosity ηE. This relationship is examined by correlating the change in MMD caused by PIB addition with the stress-dependent elongational viscosity of PIB-oil solutions as predicted by the FENE-P dumbbell kinetic theory. The increase in MMD due to PIB varies linearly with the predicted ηE at constant atomization tensile stress.
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    AIChE Journal 42 (1996) 
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  • 139
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    AIChE Journal 42 (1996), S. 1213-1219 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Rosensweig's (1979) analysis of the stability of gas-fluidized magnetically stabilized fluidized beds (MSFBs) with voidage perturbations is modified to include terms dependent on the fluid density. This allows the stability analysis to be applicable to liquid-fluidized MSFBs, which have potential use in liquid chromatography. Results show that in systems where the fluid density is not insignificant when compared to the solid-phase density, the difference in density between the two phases should be used when normalizing the magnetization required to achieve stability. Comparisons between theory and experiment show that although the present analysis improves on Rosensweig's analysis, it still does not give reliable, quantitative predictions of stability behavior. It is suggested that for liquid-fluidized MSFBs, stability to particle velocity perturbations, rather than to voidage perturbations, is more relevant to chromatographic applications wherein the purpose of magnetic stabilization is to prevent particle mixing as opposed to preventing the occurrence of bubbling and slugging observed in gas-fluidized beds.
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    AIChE Journal 42 (1996), S. 1220-1224 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new technique was developed to measure the hydraulic permeability of reinforced gel membranes and allows calculation of the Darcy permeability (κ) of the gel. It was applied to agarose with concentrations ranging from 2.0 to 7.3%. To create membranes that would be thin enough to yield easily measured filtration rates at modest applied pressures and yet withstand handling, gels were cast on woven polyester meshes. The resulting membranes had thicknesses of 70-100 μm and a fractional open area of 0.32. To correct for the presence of the mesh, finite-element solutions were obtained for the pressure field in the 3-D region occupied by the gel. For the meshes used here, the hydraulic permeability of the reinforced membrane was calculated to be 0.47-0.55 times that for a layer of pure gel, the exact value depending on the thickness of the composite membrane. The principal determinant of κ was the agarose concentration, but there was a secondary effect of applied pressure. The Darcy permeability extrapolated to zero applied pressure (κ0) varied from 616 nm2 for 2.0% agarose to 22 nm2 for 7.3% agarose. At a given gel concentration, the value for κ0 was as much as twice the value for κ measured at the maximum pressure difference of 20 kPa. This method can be adapted to a variety of other gel materials.
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    AIChE Journal 42 (1996), S. 1225-1233 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A theoretical model for the prediction of drop and bubble (fluid-particle) breakup rates in turbulent dispersions was developed. The model is based on the theories of isotropic turbulence and probability and contains no unknown or adjustable parameters. Unlike previous work, this model predicts the breakage rate for original particles of a given size at a given combination of the daughter particle sizes and thus does not need a predefined daughter particle size distribution. The daughter particle size distribution is a result and can be calculated directly from the model. Predicted breakage fractions using the model for the air-water system in a high-intensity pipeline flow agree very well with the available 1991 experimental results of Hesketh et al. Comparisons of the developed model for specific particle breakage rate with earlier models show it to give breakage-rate values bracketed by other models. The spread in predictions is high, and improved experimental studies are recommended for verification.
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    AIChE Journal 42 (1996), S. 1234-1243 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The transport of water and pentane vapor in Langmuir-Blodgett (LB) films of arachidic acid is investigated. A quartz crystal microbalance is used to monitor the mass increases of the films upon exposure to the vapor as a function of the pressure. By examining films of different thicknesses, it is shown that it is possible to measure both surface adsorption and solubility. Diffusivity is calculated from the rate of uptake. Water and pentane have Fickian diffusion coefficients of 4 × 10-12 cm2·s-1 and 1 × 10-12 cm2·s-1, respectively. The effect of both aging and annealing of the LB films on the vapor uptake is studied and it is shown that the uptake is sensitive to the state of the film.
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    AIChE Journal 42 (1996), S. 1263-1276 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The demulsification techniques investigated use preferential surface wetting to allow separation of oil and water phases in ultrafiltration and microfiltration membranes. A hydrophobic membrane allows the permeation of an oil phase at almost zero pressure and retains the water phase, even though the molecular weight of the water molecule (18) is much smaller than that of the oil molecule (198 for tetradecane, used in this study). Hydrophobic membranes having pore sizes from 0.02 to 0.2 μm were tested for demulsification of water-in-oil emulsions and water/oil/solid mixtures. The dispersed (aqueous)-phase drop sizes ranged from 1 to 5 μm. High separation rates, as well as good permeate quality, were obtained with microfiltration membranes. Water content of permeating oil was 32-830 ppm depending on operating conditions and interfacial properties. For emulsions with high surfactant content, simultaneous operation of a hydrophobic and hydrophilic membrane, or simultaneous membrane separation with electric demulsification was more efficient in obtaining complete phase separation.
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    AIChE Journal 42 (1996), S. 1244-1262 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A generalized parallel pore and surface diffusion model for multicomponent adsorption and liquid chromatography is formulated and solved numerically. Analytical solution for first- and second-order central moments for a pulse on a plateau input is used as benchmarks for the numerical solutions. Theoretical predictions are compared with experimental data for two systems: ion-exchange of strontium, sodium, and calcium in a zeolite and competitive adsorption of two organics on activated carbon. In a linear isotherm region of single-component systems, both surface and pore diffusion cause symmetric spreading in breakthrough curves. In a highly nonlinear isotherm region, however, surface diffusion causes pronounced tailing in breakthrough curves; the larger the step change in concentration, the more pronounced tailing, in contrast to relatively symmetric breakthroughs due to pore diffusion. If only a single diffusion mechanism is assumed in analyzing the data of parallel diffusion systems, a concentration-dependent apparent surface diffusivity or pore diffusivity results; for a convex isotherm, the apparent surface diffusivity increases, whereas the apparent pore diffusivity decreases with increasing concentration. For a multicomponent nonlinear system, elution order can change if pore diffusion dominates for a low-affinity solute, whereas surface diffusion dominates for a high-affinity solute.
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    AIChE Journal 42 (1996), S. 1304-1318 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two critical decisions must be made in the charging sequence of batch reactors: target setting and alarm generation. A number of statistics-based strategies are proposed in this article to perform these tasks. The off-line and on-line target setting procedures developed in this work can be adopted to increase the profit margin of any given batch process without sacrificing reliability. A synthesis method for building optimal alarm logic is also described in detail. Monitoring systems constructed according to this suggested approach are effective in reducing the probability of undetected faulty batches. Extensive simulation studies show that the proposed strategies are suitable for application of manufacturing high-value-added products, which is a prevailing practice in batch processes.
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    AIChE Journal 42 (1996), S. 1319-1325 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In-situ laser reflectance monitoring of metal-organic chemical vapor deposition (MOCVD) is an effective way to monitor growth rate and expitaxial layer thickness of a variety of III-V and II-VI semiconductors. Materials with low optical extinction coefficients, such as ZnTe/GaAs and AlAs/GaAs for a 6328 Å HeNe laser, are ideal for such an application. An Extended Kalman filter modified to include a variable forgetting factor was applied to the MOCVD systems. The filter was able to accurately estimate thickness and growth rate while filtering out process noise and cope with sudden changes in growth rate, reflectance drift, and bias. Due to the forgetting factor, the Kalman filter was successful, even when based on very simple process models.
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    AIChE Journal 42 (1996), S. 1277-1292 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Improvements in bioprocess performance can be achieved by genetic modifications of metabolic control structures. A novel optimization problem helps quantitative understanding and rational metabolic engineering of metabolic reaction pathways. Maximizing the performance of a metabolic reaction pathway is treated as a mixed-integer linear programming formulation to identify changes in regulatory structure and strength and in cellular content of pertinent enzymes which should be implemented to optimize a particular metabolic process. A regulatory superstructure proposed contains all alternative regulatory structures that can be considered for a given pathway. This approach is followed to find the optimal regulatory structure for maximization of phenylalanine selectivity in the microbial aromatic amino acid synthesis pathway. The solution suggests that from the eight feedback inhibitory loops in the original regulatory structure of this pathway, inactivation of at least three loops and overexpression of three enzymes will increase phenylalanine selectivity by 42%. Moreover, novel regulatory structures with only two loops, none of which exists in the original pathway, could result in a selectivity up to 95%.
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    AIChE Journal 42 (1996), S. 1293-1303 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A systematic and complete method to design robust predictive controllers for unconstrained linear systems is proposed. The synthesis procedure is based on rigorous theoretical foundations, without resorting to approximations or ad hoc design guidelines, yet it remains a viable tool for practical application. A significant feature is that the robust predictive controller retains the servo performance of a nominal predictive controller designed using conventional methods. In addition, the robust predictive controller can be designed to guarantee perfect steady-state rejection of asymptotically constant disturbances. The robust design method is developed for systems affected by unmodeled dynamics and is based on solving a discrete-time model-matching problem. It is shown that the robust controller can be classified legitimately as a predictive controller because it minimizes the same performance functional as the nominal predictive controller. An illustrative design example is given.
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    AIChE Journal 42 (1996), S. 1326-1340 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mass-exchange network (MEN) synthesis problem is considered with streams whose target compositions are allowed to vary between upper and lower bounds. The design task is to determine the minimum mass separating agent (utility) cost needed for the transfer of a single component from the rich to the lean streams. The mathematical formulation of this synthesis problem leads to a mixed integer nonlinear program. In this work, we propose a novel formulation of the problem that leads to a linear program. Stream decomposition is employed in attaining this novel linear programming formulation and rigorous proofs are presented which establish that the two formulations have the same solution. The linear programming formulation reduces the complexity of the considered MEN synthesis problem, thus making feasible its solution even for large-scale problems. Two examples, illustrating the procedure, are presented. Both demonstrate that significant utility cost savings can be achieved over the fixed composition MEN synthesis problem.
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    AIChE Journal 42 (1996), S. 1341-1349 
    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 is demonstrated how NMR imaging can be used noninvasively to quantify the volume of nonaqueous phase liquid (NAPL) present in an otherwise water-saturated porous medium. Data were recorded during the operation of a pump and treat (PT) remediation scheme on a bed of water-saturated sand contained within a vertical column. The model contaminant used was n-hexanol, and three different aqueous flow rates were employed. These data were then critically compared with the predictions of three models currently used to describe the dissolution of NAPL during a PT scheme: the linear mass-transfer model, the pore-diffusion model, and the shrinking-core model. The pore-diffusion model gave best agreement with the experimental data. However, none of the models predicted the observed dependence of mass transfer on Darcy velocity.
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    AIChE Journal 42 (1996), S. 1371-1378 
    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 batch pressure-response cell provides flexible and accurate means of assessing the kinetics in heterogeneous gas-liquid reactions. A new model is derived to determine the kinetics of reactions of general (n,m) order using binary gas phase. This model has an important feature that allows the determination of the reaction order with respect to the gas-phase reactant and the rate constant from a single set of pressure vs. time data through a simple two-parameter estimation routine. Gas mixing was introduced via a simple modification of the liquid-phase magnetic stirrer to reduce the gas-phase mass-transfer resistance to negligible levels and the parameter estimation problem to only two factors. The heterogeneous cobalt catalyzed sulfite oxidation reaction at low partial pressures of oxygen using a nitrogen-oxygen mixture was tested to verify the validity of the model. The predicted kinetics were remarkably close to those values in the literature, yielding an oxygen order of 1.98 ± 0.02, which is taken to be second order in oxygen.
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    AIChE Journal 42 (1996), S. 1350-1360 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A three-phase reactor model for describing the hydrotreating reactions in a trickle-bed reactor was developed. It includes correlations for determining mass-transfer coefficients, solubility data, and properties of the compounds under process conditions. The model, based on the two-film theory, was tested with regard to the hydrodesulfurization of vacuum gas oil in a new high-pressure pilot plant operated under isothermal conditions. The sulfur content of the product oil was found to depend strongly on the gas/oil flow ratio within the reactor. This is due to the inhibiting effect of hydrogen sulfide on the chemical reaction rates described by Langmuir-Hinshelwood kinetics. The poor conversion which, in contrast to industrial plants, is often observed in pilot plant reactors can be explained by incomplete catalyst wetting produced by low liquid velocities. The simulation shows a good agreement with the experiments carried out in a wide range of temperature, pressure, space velocity and gas/oil ratio.
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    AIChE Journal 42 (1996), S. 1361-1370 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nitrogen-atom behavior in a low-pressure, nonisothermal microwave-generated nitrogen afterglow was studied. N-atom flux was measured by chemical titration. It was found that an increase in power or flow rate, or a decrease in pressure resulted in larger productions of N atoms. A one-dimensional mass-continuity equation was used to model N atoms' concentration field in the afterglow. The model, with no adjustable parameters, agreed closely with experimental measurements. The model shows that convection, diffusion, and wall recombination play important roles in the afterglow. In contrast, N-atom generation and homogeneous recombination are of marginal importance. The model was manipulated to assess the impact of the measuring technique, chemical titration, on the N-atom flux. It was found that the N-atom flux profile is only slightly impacted, although the concentration profile is strongly modified.
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    AIChE Journal 42 (1996), S. 1379-1387 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The reaction rate of methanol was measured in solutions of sodium chlorate and sulfuric acid at several levels of temperature and concentration, in the presence of mercuric nitrate. The progress of the reaction was monitored by proton NMR signals corresponding to methanol and formic acid. Chlorine dioxide formation was suppressed by adding mercuric nitrate, which was shown earlier to catalyze the disproportionation of the intermediate species, chlorous acid, and sequester chloride ions. The reaction is first order in methanol and chlorate concentration and in the Hammett acidity function. The reaction of formic acid, sodium chlorate and sulfuric acid was also studied using the same technique. Formic acid was stable and did not react with chlorate at a measurable rate, even at concentrations and temperatures of a commercial process. This study relates to commerical processes that produce chlorine dioxide by reducing chlorate ions with methanol.
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    AIChE Journal 42 (1996), S. 1388-1396 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Bubble instabilities observed in film blowing using four different polyolefins are discussed: high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and polypropylene (PP). Special attention is given to the effect of the frost line height on the bubble stability, an effect mostly ignored in the literature. A video-camera system was used to record the bubble shape and oscillations. In general, three forms of instabilities and combinations were observed: (1) axisymmetric periodic variations in the bubble diameter; (2) helical motions of the bubble; and (3) variations in the position of the solidification line. The four resins show different stability behaviors. The LDPE has the most stable operating space and the PP is the most unstable one. No correlation was observed between bubble stability and oscillatory shear rheological properties of the resins. Instability is enhanced by increasing take-up ratio, increasing blow-up ratio, and decreasing frost line height. Furthermore, for the LDPE, some operating points were not attainable and multiple steady states were observed. Our results are in a poor agreement with the predictions Cain and Denn's 1988 analysis.
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    AIChE Journal 42 (1996), S. 1416-1424 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Structural Characteristics of mono- and distearin mixed monolayers spread on aqueous solutions containing sugar (glucose or sucrose) at 0.5 mol/L were studied as a function of temperature and interfacial and subphase compositions. The compression isotherms were obtained using an automated Langmuir-type film balance over a temperature range of 10 to 40°C. The results show an expansion in the structure of the mixed monolayer with sugar in subphase. Nonideal mixing of the component at interface was observed with positive deviation from the additivity rule. This fact is indicative of the presence of repulsive interactions between the two lipids on sugar aqueous solutions. The mixed monolayers with a monostearin molar fraction less than 0.8 are stable from a thermodynamic point of view. Mixed monolayer stability depends on monolayer composition, temperature, and surface pressure with different order of magnitude.
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    AIChE Journal 42 (1996), S. 1407-1415 
    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 statistical reconstruction of lattice models of real porous media is one of the basic engineering problems in the theory of porous structure and has a variety of applications in the study of transport, in mineral processing, and in material characterization. A systematic analysis of the reconstruction problem of porous media is presented, as well as a closed-form solution. The solution is presented in the form of a linear filter acting on Gaussian processes by means of a superposition of elementary correlated processes with prescribed correlation properties, and in the form of a memoryless process recalling the theory of Khinchin on the properties of correlation functions. The connection of this approach with models of correlated percolation is also discussed.
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    AIChE Journal 42 (1996), S. 1397-1406 
    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 electrophoretic motion of a dielectric sphere along the centerline of a long circular cylindrical pore is studied theoretically. The imposed electric field is constant and parallel to the nonconducting pore wall, and the particle and wall surfaces are assumed uniformly charged. Electrical double layers adjacent to solid surfaces are assumed to be thinner than particle radius and gap width between surfaces. The presence of the pore wall affects particle velocity: 1. an electroosmotic flow of the suspending fluid exists due to interaction between the electric field and the charged wall; 2. the local electric field on the particle surface is enhanced by the insulated wall, speeding up the particle; and 3. the wall increases viscous retardation of the moving particle. To solve electrostatic and hydrodynamic governing equations, general solutions are constructed from fundamental solutions in both cylindrical and spherical coordinate systems. Boundary conditions are enforced at the pore wall by Fourier transforms and then on the particle surface by a collocation technique. Typical electric-field-line, equipotential-line and streamline patterns for the fluid phase are exhibited, and corrections to the Smoluchowski equation for particle electrophoretic velocity are presented for various relative separation distances between the particle and wall. The presence of the pore wall always reduces the electrophoretic velocity; however, the net wall effect is quite weak, even for very small gap width between the particle and wall.
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    AIChE Journal 42 (1996), S. 1434-1442 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Microtubules are linear polymers of the cytoskeleton that serve to organize the cytoplasm of eukaryotic cells. Understanding how microtubule polymers self-assemble is important in biotechnology, including the development of novel cancer therapies and proper guidance of regenerating neurons. The assembly of microtubules occurs by a unique process whereby an individual microtubule undergoes abrupt and apparently stochastic switching between alternating steady states of growth and shrinkage, a phenomenon known as microtubule dynamic instability. To characterize these oscillations spectral (frequency-domain) analysis, commonly used in engineering for system identification, was applied. Power spectra of the individual microtubule-length life histories revealed oscillations within growth phases, directly reflecting acceleration and deceleration in the growth process. These fluctuations were not accounted for by the standard two-state model commonly used in the analysis of microtubule assembly, despite the inclusion of simulated measurement error in the model. Thus, the spectral analysis of microtubule assembly permitted characterization of assembly process dynamics independent of particular assembly models, and as such represents a powerful analytical framework within which to study microtubule dynamic instability and assess its function in vivo.
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    AIChE Journal 42 (1996), S. 1425-1433 
    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 surface tension of organic compounds, σ = [ P·(ρl - ρv)]4 is proposed where P = P0·(1 - Tr)0.37·Tr·exp(0.30066/Tr + 0.86442·Tr9). ρl and ρv are molar densities of liquid and vapor, respectively, Tr = T/Tc, and P0 is a temperature-independent, compound-dependent constant similar to Sugden's parachor. This new expression, derived from statistical-mechanics, represents the experimental surface tension data of 94 different organic compounds within 1.05 AAD%. We also propose P0 = 39.6431· [0.22217 - 2.91042 × 10-3·(R*/Tbr2)·Tc13/12/Pc5/6] as a corresponding-states expression to correlate the temperature-independent parameter P0 for various compounds. Here, R* = Rm,ref, Rm is the molar refraction, Rm,ref is the molar refraction of the reference fluid (methane), and Tbr is the reduced normal boiling point. When this generalized expression is used, surface tensions for all 94 compounds can be predicted within 2.57 AAD% at all temperatures investigated.
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    AIChE Journal 42 (1996), S. 1443-1453 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Expression of proteins in eucaryotic systems is often the only way to ensure the correct folding and processing necessary for protein function. Heterologous proteins, however, are commonly retained in the secretory pathway, so that secreted product yield is low despite a high level of transcription. A major limiting step in protein secretion is protein folding in the lumen of the endoplasmic reticulum. This process is assisted by accessory macromolecules resident in this compartment, including chaperones such as the hsp70 homologue binding protein (BiP). Although induction of foreign proteins in yeast initially elicits a transient increase in local chaperone concentration, long-term protein expression lowers both chaperone and secreted product. A mechanistic model that can account for the experimentally observed role of BiP in secretion and the effects of BiP overexpression on the secretory pathway is described here. The model predicts that equimolar synthesis of chaperone and foreign protein should optimize protein secretion.
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    AIChE Journal 42 (1996), S. 1454-1464 
    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 of determining control coefficients and pseudo-first-order kinetic parameters is presented for cell growth, substrate consumption, and product formation in a chemostat bioreactor. From the equations that relate the control coefficients to process variables, such as feed concentrations of the limiting substrate and the product of interest, a perturbation method is developed to determine control coefficients from steady-state measurements. This method combined with the transient response analysis provides a practical way for determining control coefficients and estimating kinetic properties in chemostat bioreactor systems. To determine the kinetic parameters, one measures cell mass, concentrations of the limiting substrate and the product of interest following a step change in the feed concentration until the system reaches a new steady state. The time courses of these variables are processed to obtain control coefficients, which yield the pseudo-first-order kinetic constants for cell growth, substrate consumption, and product formation. Only steady-state responses are needed in calculation, if a step change in cell concentration in the feed stream can also be introduced without significantly perturbing cell physiology. This method is useful in characterizing the kinetics of whole cell bioreactions: results from chemostat experiments can be used to design operating strategies for batch or fed-batch bioreactions. It is generally applicable to continuous-stir-tank reactors with interacting parallel reactions.
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    AIChE Journal 42 (1996), S. 1465-1476 
    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 rotating disk apparatus was used to study the removal of C14 labeled docosanoic (behenic) acid from stainless steel. The liquid cleaning behavior was studied as a function of temperature, surface morphology, and fluid flow. A mass-transfer model was proposed to describe the removal of behenic acid from stainless steel using a rotating disk apparatus. The cleaning rates computed from the mass-transfer model were compared with experimental observations; it was found that at low temperatures the removal was a function of rotation speed. At higher temperatures, however, the removal rate was independent of the disk rotation speed. In some cases the predicted rate of behenic acid removal differed significantly from the observed data. A plausible explanation for these variations is that the residues are removed by the combined effects of dissolution and the shearing of large clusters of solid behenic acid crystals. The temperature-dependent behavior of the cleaning data was analyzed using an activation-energy-based model.
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    AIChE Journal 42 (1996), S. 1477-1480 
    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 42 (1996), S. 1481-1486 
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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 42 (1996), S. 1487-1490 
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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 42 (1996), S. 1495-1499 
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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 42 (1996), S. 1500-1500 
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    AIChE Journal 42 (1996), S. 1491-1494 
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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 42 (1996) 
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    AIChE Journal 42 (1996), S. 1501-1513 
    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 flow in a single-cavity extrusion die is considered by using 1-D equations. Since the fluid flow in a well-performing die does not deviate much from the case of perfect widthwise distribution, linearization of 1-D governing equations is often justified. It is demonstrated how linearization can lead to significant simplifications in the analysis of die flow. A self-consistent asymptotic expansion is identified to accomplish this linearization; the expansion can be generalized to obtain higher-order corrections if necessary. In contrast to previous analyses, which have generally been numerical, analytic solutions are obtained to predict widthwise flow nonuniformities in a die having a specific cavity area variation and in which cavity inertial effects are important; these solutions are valid for power-law and Newtonian fluids. A novel truncated power-law approach to modeling the flow of shear-thinning fluids in a die is proposed that combines, by using analytical criteria, the solutions for purely Newtonian or power-law flow in the cavity and slot. The validity of this approach is demonstrated through comparison with numerical results of a 1-D die model for a Carreau constitutive equation.
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    AIChE Journal 42 (1996), S. 1536-1546 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Axial solid velocity, solid volume fraction, and solid shear viscosity were computed in the riser of a circulating fluidized-bed reactor using a two-phase 2-D computational fluid dynamic model. The time-averaged model predictions agree well with the experimental data of Miller and Gidaspow (1992). The model predicts a core-annulus flow in the riser, similar to that found experimentally. The maximum velocity in the core agrees well with the measurements, but the downflow in the annulus is somewhat overpredicted. The solid volume fractions profiles agree well in both core and annulus, with discrepancy in the core at the level close to the inlet. The radial profile of solid shear viscosity computed by the turbulent kinetic energy model is ten times lower in the core than that found experimentally, but with a linear function of solid volume fraction in the measurement, the computed profile agrees well with experiments.
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    AIChE Journal 42 (1996), S. 1514-1524 
    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 and mass transfer from a circular cylinder exposed to a convective environment with a surface reaction of arbitrary order is studied based on the stream function-vorticity formulation. A hybrid numerical scheme combining the Fourier spectral method in the angular direction and the spectral element method in the radial direction is used to solve the conservation equations along with an influence matrix technique to resolve the vorticity boundary conditions. Results showing the temporal evolution of the flow, temperature and concentration fields are presented for cases with and without vortex shedding with the latter triggered by the cylinder's rotation. A parametric study is also performed to examine the influence of the Reynolds number, Grashof number, Prandtl number, Schmidt number, Damköhler number, the reaction order, the flow alignment, the heat of reaction, the rotational velocity and the flow pulsation on the effectiveness of the reaction surface. With the exception rotation, they all exhibit strong dependence.
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    AIChE Journal 42 (1996), S. 1525-1535 
    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 concerns some selected 3-D flow effects on residence time distribution (RTD) in a screw extruder. The Newtonian problem is emphasized in which the cross- and down-channel flow components can be formally discoupled and treated as two parallel 2-D problems: our stream-function-based analysis of the Newtonian cross-channel flow was combined with the existing 2-D solution for the down-channel flow. The RTD was determined by tracing the streamlines generated from both velocity components for the industrially important cases of fully- and partially-filled channels. The effect of the cross-channel flow on the RTD is discussed in connection with the stagnation flows, the down-channel pressure gradient, and the presence of a free surface in a partially-filled channel. The cross-channel pressure distribution is compared to the conventional 1-D theory. The non-Newtonian effects were assessed using the commercial software POLYCAD.
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    AIChE Journal 42 (1996), S. 1547-1552 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Transient drop-size distributions of stirred dispersions undergoing breakage were experimentally measured at long stirring times. The results show that drops continue to break the entire duration of the experiment (at least up to 10 h) and force a reevaluation of the widely held concept of a maximum stable drop diameter, dmax. Transient distributions show the existence of self-similarity, which is the same as that observed in transient distributions obtained at short times (up to ∼ 1 h, Sathyagal et al., 1995b) indicating that the nature of breakage does not change with time. The existence of similarity at long stirring times can be used to obtain good estimates of breakage rates of small drops by an inverse problem procedure.
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    AIChE Journal 42 (1996), S. 2941-2947 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pulsed-tracer experiments conducted for horizontal gas flow through a horizontal duct of rectangular cross section (height = 12.7 mm) containing powder in the coherent-expanded vibrated-bed state have been reported (Benge and Squires, 1995; Squires and Benge, 1995). Axial gas dispersion in the duct can be treated by a simple model: the dispersion is a “spreading” superimposed on plug flow, with no gas bypassing and no lagging gas indicative of dead zones. At a given weight hourly space velocity, a large variation in axial Peclet number (Peax) can be achieved by varying length of duct and gas superficial velocity in proportion, with no substantial effect upon gas-solid contacting efficiency. Herein, we report data for the methanol-to-olefin reaction conducted in three ducts at lengths affording Peax-values from ∼ 2 to ∼ 20. The new data display a trend in light-olefin yield vs. Peax similar to that reported earlier for three fluid-bed reactors at diameters of 10, 102 and 600 mm.
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    AIChE Journal 42 (1996), S. 2984-2986 
    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 42 (1996), S. 2990-2992 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 42 (1996) 
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    AIChE Journal 42 (1996), S. 3030-3040 
    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 and operational performance of convective industrial dryers are an important field of chemical engineering, which is still governed by empiricism. This article addresses the design vs. operation problem for three basic types of continuous convective industrial dryers: conveyor-belt, fluidized bed, and rotary. Design procedures determined the optimal construction and operational characteristics in terms of total annual cost for each type involved and for a given production capacity through appropriate mathematical modeling. All dryer were compared by evaluating optimum configurations for a wide range of product characteristics and production capacity values. Once the dryer configuration was specified, its operational performance was evaluated by comparing the optimum operational cost vs. production capacity for predefined optimum designed structures. Rotary dryers were more expensive to design than fluidized bed dryers. Operationally, however, it is the other way around due to the favored heat transfer achieved in rotary dryers. Conveyor-belt dryers lie somewhere between producing satisfactory results in terms of both design and operation. Case studies on foods and inorganics are included to demonstrate the performance of each process as well as the effectiveness of the proposed approach.
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    AIChE Journal 42 (1996), S. 3063-3086 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This article deals with distributed parameter systems described by first-order hyperbolic partial differential equations (PDEs), for which the manipulated input, the controlled output, and the measured output are distributed in space. For these systems, a general output-feedback control methodology is developed employing a combination of theory of PDEs and concepts from geometric control. A concept of characteristic index is introduced and used for the synthesis of distributed state-feedback laws that guarantee output tracking in the closed-loop system. Analytical formulas of distributed output-feedback controllers are derived through combination of appropriate distributed state observers with the developed state-feedback controllers. Theoretical analogies between our approach and available results on stabilization of linear hyperbolic PDEs are also identified. The developed control methodology is implemented on a nonisothermal plug-flow reactor and its performance is evaluated through simulations.
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    AIChE Journal 42 (1996), S. 1627-1632 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new approach for the determination of concentrations in the case of nonequilibrium washing stages is presented. Each washing stage is assumed to consist of series of mixing cells, and the conservation of solute mass is solved by Laplace transformation. The simplicity of the resulting equations makes this approach more practical than the existing one.
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    AIChE Journal 42 (1996), S. 1633-1641 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The graphical construction called an energy-utilization diagram (EUD) is adopted for analyses of energy transformation and exergy losses in a distillation column. The overall exergy loss on one plate of a column can be decomposed into six kinds of exergy losses and are represented graphically. Two of them are caused by mixing and cooling in the vapor phase, and the other two by mixing and heating in the liquid phase. To display the remaining two yielded by condensation and evaporation of each component, the concept of the individual energy level is applied. The relationship between the individual energy level and the xy diagram is presented as well as effects of the reflux ratio and the feed location on the EUD for the whole column. Separation of n-hexane and n-octane is used to illustrate the methodology.
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    AIChE Journal 42 (1996), S. 3164-3169 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The hyperbolic nature of the continuity equation in the melt spinning process causes several kinematic waves to travel in the spinline. Since different traveling waves possess different speeds, the system invariably has many characteristic times. This study computes the traveling times of these waves, finds their interrelationships, and then derives the criterion for the instability of periodic oscillation known as draw resonance. The period of oscillation is greater than the fluid residence time, but equal to the time during which both the maximum and minimum spinline cross-sectional area waves travel in sequence from the spinneret to the take-up. The onset of draw resonance occurs when two successive unity-throughput waves are also able to travel the same distance within the same period of oscillation. This happens when the drawdown ratio takes on the critical value of 20.218 for the isothermal spinning of Newtonian fluids, agreeing with the value reported by earlier researchers.
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    AIChE Journal 42 (1996), S. 3153-3163 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetics of silica particle formation by the ammonia-catalyzed hydrolysis of tetraethyl orthosilicate (TEOS) in water-in-oil (W/O) microemulsions containing a nonionic surfactant was investigated using Fourier-transform infrared spectroscopy, transmission electron microscopy, and light-scattering techniques. The results show that TEOS hydrolysis and silica-particle growth occur at the same rate, indicating the growth of silica particles is rate-controlled by the hydrolysis of TEOS. The rate of TEOS hydrolysis in microemulsions is first order with respect to the concentration of aqueous ammonia (29 wt. % NH3), but depends weakly on the concentration of water. Based on the fact that TEOS hydrolysis follows a nucleophilic (SN2) substitution of the TEOS's ethoxy group with hydroxyl ion, the kinetic data suggest that both water and ammonia remain predominately in W/O microemulsion droplets. The rate of TEOS hydrolysis also depends on the surfactant concentration that controls the molecular contact between hydroxyl ions and TEOS in the solution. Due to the reaction-controlled growth mechanism, the silica-particle size distribution retains virtually the same shape over the growth period. The final average size of silica particles can be varied from 26 to 43 nm by adjusting concentrations of water and surfactant. Increasing the water concentration decreases the average size and uniformity of silica particles. For a given water concentration, the smallest and most uniform silica particles are produced at intermediate water-to-surfactant molar ratios (about 1.9). The results are discussed in terms of the effect of water concentration on the stability of the hydrolyzed silica reacting species during the nucleation of particles and of the water-to-surfactant molar ratio on the compartmentalization of silica species in microemulsions.
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  • 187
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    AIChE Journal 42 (1996), S. 3202-3211 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Increased demand for cryocoolers for aerospace and terrestrial applications has served as an incentive over the past decade to develop units with specific performance parameters. Since many of these units also require a high degree of reliability, considerable effort has been directed toward meeting this goal. The excellent progress that has been made is summarized, and there is every indication that the use of cryocoolers will expand greatly during the next decade, with a rapid transition from present aerospace/military applications to highly civilian uses in such areas as medicine, electronic transmission, environmental control, energy storage, and transportation.
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  • 188
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    AIChE Journal 42 (1996), S. 3231-3240 
    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 segment-based molecular thermodynamic model for the Gibbs energy of polymer solutions or oligomer solutions is used to represent the Gibbs energy of mixing for aqueous nonionic surfactant solutions. In contrast to the mass-action models and pseudophase models, which are often discussed in the literature, the Gibbs-energy model provides an explicit account of the solution nonideality, including activity coefficients of monomeric amphiphiles in the aqueous phase. The equilibrium between monomeric amphiphiles and micellar amphiphiles is described by the equal-activity relationship. The Gibbs-energy model makes it possible to use a well-accepted molecular thermodynamic framework to correlate and represent phase behaviors of aqueous nonionic surfactant solutions.
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  • 189
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    AIChE Journal 42 (1996), S. 1685-1696 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model and numerical code for the simulation of contaminant removal from soils by electric fields are applied in two dimensions. The model describes the coupled transport of mass and charge, and the chemical speciation of a multicomponent system subjected to an electric field. Transport mechanisms included are electroosmosis, pressure-driven convection, electromigration, and diffusion. The model can also describe complexation, dissolution and precipitation reactions, surface complexation and sorption processes, and electrochemical reactions. Chemical and sorption equilibria are assumed. Transport equations used are based on quantities conserved throughout chemical reactions so that only the time scales of transport processes need to be resolved. The model is used to simulate the removal of phenol from kaolin clay for which experiments are presented. The successful explanation of the experimental observations confirms the theoretical bases of the model.
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  • 190
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    AIChE Journal 42 (1996), S. 1697-1705 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Catalyst effectiveness factors provide a quantitative estimate of diffusion resistance for chemical reactions in porous particles. The objective of this research is to develop an approach to calculate liquid-phase, porous-particle effectiveness factors, which are based on spherical reactant molecules and cylindrical pores that both have size distributions. Reactants larger than a given pore are excluded from the pore. A first-order reaction occurs when reactant molecules diffuse into pores that hinder their movement due to steric interactions with the pore wall. The reactant size distribution is described by rectangular or gamma distributions, and the pore-size distribution is modeled by continuous rectangular or discrete fractal distributions. Effectiveness factors are defined and evaluated for (a) one-size reactants in one-size pores, (b) all reactants in one-size pores, (c) one-size reactants in all pores, and (d) all reactants in all pores. Most of the discussion deals with equal-length pores, but the effect of a distribution of pore lengths is also considered.
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  • 191
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    AIChE Journal 42 (1996), S. 3364-3372 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Three binary vapor-liquid equilibrium (VLE) data were measured: tertbutanolethanediol, tertbutanol-KAc, and ethanediol-KAc. Experimental data were correlated with the salt-containing local composition model (SCLCM). For the multicomponent system, VLE data predicted by SCLCM are in agreement with the data in the literature. An industrial plant (3500T/Y) of salt-containing extractive distillation for the tertbutanol/water/ethanediol/potassium acetate system was simulated by SCLCM and improved the Rose relaxation method. Simulation results agree well with industrial data.
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  • 192
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    AIChE Journal 42 (1996), S. 3388-3402 
    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 to analyze the closed-loop stability of a system composed of a nonlinear process and a discrete controller is developed. The closed-loop system is described by a set of difference equations resulting from the discretization of the continuous-time model. A commonly used method of discretization (forward difference) offers an incorrect relative order compared to exact discretization. The state and input sensitivity equations of the continuous-time model are used in computing the nominal closed-loop stability criteria. The nominal stability analysis is extended to the important cases of unmeasured states and uncertain model parameters. A numerical Lyapunov function is used to estimate closed-loop regions of attraction. A simulation example (a CSTR with input multiplicity) presented illustrates the analysis methods and closed-loop behavior.
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  • 193
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    AIChE Journal 42 (1996), S. 3212-3222 
    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 class of mixing rules, with van der Waals one-fluid mixing rule and second virial coefficient constraints, was developed for cubic equations of state (EOS) for application to various asymmetric, highly nonideal chemical systems. This approach evolved from previous research in the EOS field. The resulting mixing rule is practical in application, yet more flexible than Huron-Vidal or Wong-Sandler mixing rules and depends only on composition and temperature. It also avoids the problems associated with the Wong-Sandler mixing rules. A cubic EOS with the new mixing rules was applied successfully to complex mixtures. The new rules reduce to van der Waals mixing rules when the parameters in the nonrandom excess Helmholtz free energy are set to zero. Since many times the classic mixing rules worked very well for nonpolar systems, it is extremely desirable that the composition-dependent mixing rules reduce to the classic mixing rules. Preserving this capability also ensures that the binary interaction parameters for the classic quadratic mixing rules in the DECHEMA Chemistry Data Series for mixtures of low boiling substances and other existing databases for systems involving hydrocarbons and gases can be used directly in the new EOS mixing rules, in addition to liquid-activity coefficient model parameters currently reported in the Series.
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  • 194
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    AIChE Journal 42 (1996), S. 1723-1740 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Although experimental vapor pressures are abundant in the medium-pressure range (psat ≃ 5-100 kPa), their values are scarce and uncertain at lower pressures due to experimental difficulties in determining the data. Reliable values are, however, required by technology (separation processes dealing with mixtures containing high molar mass compounds) and environmental concerns (transport and fate of high-boiling pollutants). The ability of frequently used vapor-pressure equations to extrapolate the data at medium pressures toward the triple-point temperature was tested on three groups of compounds (polar and nonpolar organic chemicals, n-alkanes, and 1-alkanols) for which reliable experimental data in the low-pressure range were available. Results of a simple extrapolation were compared with those from a simultaneous correlation of vapor pressures in the medium-pressure range and the differences between heat capacity of an ideal gas and that of the liquid available at lower temperatures. The latter is generally more reliable, as it is controlled by the exact thermodynamic constraints linking vapor pressures and the thermal data. The extent of improvement when using simultaneous correlation was examined, as well as the influence of the quality of input data on the results of extrapolation. Extrapolated values were compared with experimental vapor pressures and calorimetric enthalpies of vaporization that were selected from literature and free of any important systematic errors.
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  • 195
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    AIChE Journal 42 (1996), S. 1753-1764 
    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 thermodynamic micellization model is proposed for the description of asphaltene precipitation from petroleum fluids. It describes the solubilization of asphaltene polar species by resin bipolar molecules in the micelles. A simple form of the standard Gibbs free energy of micellization is used. The petroleum fluid is assumed to be a dilute solution with respect to the monomeric asphaltenes, resins, and micelles. The Peng-Robinson equation of state (PR-EOS) is applied to describe the fugacity of monomeric asphaltene in the bulk of the petroleum fluid. Intermicellar interactions as well as osmotic pressure effects are neglected. The proposed model shows promising results to describe asphaltene deposition from crude mixtures. It predicts the change in precipitation power of different alkane precipitants and the effect of pressure on asphaltene precipitation. The amount and the onset of predicted asphaltene precipitation are sensitive to the amount of resins in the crude. All these results are in line with laboratory observations and oil-field data.
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  • 196
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    AIChE Journal 42 (1996), S. 3508-3522 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A molecular model based on the integral equation theory of statistical thermodynamics is used to study phase separation in PEG-salt aqueous two-phase systems. PEG molecules are modeled as hard spheres that attract each other through a temperaturedependent Yukawa potential, which mimics the effect of PEG-water hydrogen bonding on the attraction between PEG molecules. The salt ions are modeled as charged hard spheres interacting through a Coulombic potential. Excess thermodynamic properties due to Coulombic and Yukawa interactions are calculated by analytical solutions to the Ornstein-Zernike equation for the mean spherical approximation closure. Yukawa parameters for PEG-PEG interactions are determined by fitting the theoretical phase diagram for a pure Yukawa fluid to the experimental phase diagram for a PEG-water mixture. The model predicts experimentally observed trends: increasing the temperature increases the slope and length of the tie lines; increasing the PEG molecular weight increases the miscibility gap; and increasing the anion charge lowers the salt concentration at which phase separation occurs. Theoretical results allow us to infer the relative importance of ion-PEG interactions, ion-solvent interactions, and the interpenetrable nature of PEG molecules on the phase separation in PEG-salt aqueous two-phase systems.
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  • 197
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    AIChE Journal 42 (1996), S. 1801-1814 
    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 carry out rapid precipitation on a practical scale, the use of a two-impinging-jets (TIJ) mixer was explored in terms of its ability to deliver rapid micromixing. The two-step Bourne reaction scheme between 1-naphthol and diazosulfanilic acid was used to characterize micromixing in the TIJ mixer as a function of hydrodynamics and mixer geometry. The characteristic time for micromixing in this device was at least as small as 65 ms. The larger the jet diameter, the higher the jet Reynolds number required to achieve the same micromixing quality. The micromixing time in the TIJ mixer correlated well as a function of a Damkohler number that led to a scale-up criterion giving an inverse relationship between the micromixing time constant and the 1.5 power of the jet velocity. Finally, the precipitation of Lovastatin was carried out in the TIJ mixer under well and poorly micromixed conditions. The level of micromixing in the precipitator affected the crystal size distribution of the precipitated product only when the time constant for micromixing was comparable to or larger than the induction time for nucleation of the solute.
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  • 198
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    AIChE Journal 42 (1996), S. 1824-1832 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Steady flow and viscoelastic properties of mixed-polysaccharides and mixed-polysaccharide-thickened oil-in-water emulsions are investigated with a cone-and-plate system using a controlled-stress rheometer. The mixed-polysaccharide system studied is xanthan gum and guar gum. The rheological properties of the mixed-polysaccharide systems exhibit strong synergistic effects. For a total polysaccharide concentration of 0.75 wt. % investigated, the synergistic effect is maximum at a xanthan:guar ratio of 15:85. The oil-in-water emulsions, prepared from a mixed-polysaccharide system as the suspending medium, are strongly shear thinning and highly viscoelastic in nature. The rheological parameters such as apparent viscosity, storage, and loss moduli increase with an increase in the oil concentration of the emulsion.
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  • 199
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    AIChE Journal 42 (1996), S. 1833-1843 
    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 experimental study examines 2-D effects on long plate drying due to heat and moisture transfer through boundary layers and porous medium interaction. Many innovative techniques are used to measure accurately boundary layers (velocity, temperature, moisture), the wall surface (infrared sensors for temperature and moisture), and the medium (water content). Gradual decrease in surface saturation measured for several kinds of materials shows that their behavior is more complex than described by the Suzuki-Maeda model, which does not predict the mass exchange sufficiently. Based on the analysis of the transfer between the surrounding air and the porous medium at the scale of the pore on a rough surface, a flow classification is defined and other characteristics are proposed. The drying rate depends on the mass-transfer coefficient, which varies along the plate with the air flow. The study of boundary layers gives the corresponding profiles with an acceptable accuracy. The laminar-to-turbulent transition increases mass-transfer rates resulting in two drying fronts. The diffusive model proposed here predicts a gradual change in the drying rate along the plate similar to the experimental one.
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  • 200
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    AIChE Journal 42 (1996), S. 1844-1852 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Membrane distillation is a membrane process in which two liquid phases at different temperatures are separated by a microporous hydrophobic membrane. The membrane plays the role of physical support for the vapor-liquid interface. Pure water transport through PTFE and PVDF flat membranes was studied, as well as the dependence of the phenomena on average temperature and recirculation rate at membrane sides. The influence of these operating conditions on mass transfer is also discussed, taking into account mass and heat transfer within the membrane and adjoining liquid phases. The concept of temperature polarization introduced into the transport equations shows its importance in experimental results.
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