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  • 1990-1994  (3,294)
  • 1925-1929
  • Chemical Engineering  (3,294)
  • 101
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 849-861 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A systematic methodology applicable to the optimal design of stable process systems is presented. It is based on the formulation of a parametric problem that provides bounds on the optimal stable solution and an iterative algorithmic approach that attains convergence of the bounds in a finite number of iterations. The bounds on the optimal stable solution are based on analytical expressions of bounds on the eigenvalues of the Jacobian matrix using the concept of the measure of the matrix. When extended to the synthesis problem of reactor networks, the approach is able to couple the optimization problem with stability issues even in cases where the number of reactors is large and the reaction mechanism is described by a general complex reaction scheme. Furthermore, since at the synthesis level the reactor network represents an exhaustive superposition of the existing structural and operational alternatives, the approach fully exploits these alternatives and coordinates a weighted optimal search that improves the objective and accommodates a stable reactor network. This approach is not restricted to the synthesis of reactor networks and can be applied to the design of total process flowsheets.
    Additional Material: 9 Ill.
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  • 102
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 870-877 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Oxidative coupling of methane was conducted by using membrane reactors. The nonporous membrane film that consisted of PbO modified by alkaline or alkaline earth compound was supported on porous SiO2-Al2O3 tube. Higher hydrocarbons were successfully synthesized with high selectivity (about 90%). A kinetic analysis was conducted to clarify whether oxide ion transportation through PbO film participated in the oxidative coupling of methane. The evaluated value of the diffusion coefficient of oxide ion transport based on the methane oxidation agreed well with that of published data. The simulated gradient of the oxide ion concentration through the PbO membrane agreed well with that measured by electron probe X-ray microanalyzer. A transient response simulated by using kinetic parameters evaluated from steady-state analysis also agreed well with the experiment. These results prove the validity of the reaction model that consists of surface reactions of methane with oxide ion which is transferred from inside to outside of the membrane reactor. Alkali modifiers on the PbO membrane surface exhibited a promotional effect on the surface reaction of methane coupling. Another membrane reactor containing Bi2O3 showed higher activity than the PbO membrane.
    Additional Material: 17 Ill.
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  • 103
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 908-910 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 104
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 899-907 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Optimal control strategies for maximizing the production of induced foreign protein by recombinant bacteria were sought by the optimal control theory. Nutrient and inducer feeding rates were selected as key control variables. Since the problem is linear in the control variables, the optimal control is bang-bang or singular. Singular solutions are shown to exist. The optimal control theory showed that the specific growth rate with respect to nutrient concentration must be kept in its maximum phase and that there exist both a cell growth period and a protein production periods. The optimal control theory calculates exactly the growth and production periods. The glucose concentration is controlled along a singular are to give a maximum specific growth rate. The inducer level is controlled along a separate singular arc.
    Additional Material: 6 Ill.
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  • 105
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 911-911 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 106
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 935-943 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Equilibrium and kinetic data for adsorption of trace CF2Cl2 (Freon-12) from various carrier gases on BPL activated carbon are reported. Coadsorption of the bulk carrier gas can severely reduce the equilibrium adsorption capacity and adsorptive mass-transfer coefficient of strongly adsorbed CF2Cl2. The difference in size between CF2Cl2 and the bulk carrier gas molecules plays a major role in establishing the binary or multicomponent equilibrium adsorption properties. The multisite (single and multicomponent) Langmuir model, which accounts for differences in adsorbate sizes, provides a reasonable framework for describing the size effects. The adsorptive mass transfer of CF2Cl2 under the experimental conditions investigated is dominated by surface diffusion into the pores of the activated carbon. The surface diffusivity is a strong function of the extent of coverage and strength of adsorption of the bulk components.
    Additional Material: 8 Ill.
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  • 107
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 956-956 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 108
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 966-979 
    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 dynamic behavior of processing systems exhibits both continuous and significant discrete aspects. Process simulation is therefore a combined discrete/continuous simulation problem. In addition, there is a critical need for a declarative process modeling environment to encompass the entire range of processing system operation, from purely continuous to batch. These issues are addressed by this article.A new formal mathematical description of the combined discrete/continuous simulation problem is introduced to enhance the understanding of the fundamental discrete changes required to model processing systems. The modeling task is decomposed into two distinct activities: modeling fundamental physical behavior, and modeling the external actions imposed on this physical system. Both require significant discrete components. Important contributions include a powerful representation for discontinuities in physical behavior, and the first detailed consideration of how complex sequences of control actions may be modeled in a general manner.
    Additional Material: 12 Ill.
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  • 109
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1046-1054 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Ion exchange equilibria of ultrathin Langmuir and Langmuir-Blodgett films of stearic and arachidic acids in contact with aqueous electrolyte solutions were studied experimentally and theoretically. A model considering electrochemical and thermodynamic aspects of the adsoption of protons, calcium, and cadmium ions from solution to the film has been developed. Key parameters are the binding constants (K's) of ions and the mixing characteristics (or Flory-Huggins interaction parameters x's) of ions in the two-dimensional film lattice plane. The ternary system can be described by the parameter values determined with binary proton-calcium ion, proton-cadmium ion, and calcium-cadmium ion systems: KCa = 2.9 × 102, KCd = 8.6 × 103, KH = 3.6 × 106, χH - Ca = -0.76, χH-Cd = 0.13, and χCa-Cd = 1.0. Competitive ion adsorption was measured by FTIR ATR spectroscopy of either collapsed or ordered LB films. Data for the proton-calcium-cadmium ion system agreed well with the model predictions. The results show possible future applications of such thin films as ion sensors or ion exchange materials.
    Additional Material: 9 Ill.
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  • 110
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1067-1081 
    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 denaturation, common in hydrophobic adsorption systems, causes misinterpretation of adsorption mechanisms, interferes with analysis in analytical chromatography, and complicates the design of large-scale adsorption processes. A detailed adsorption model isolates the effects due to denaturation from those due to mass transfer and intrinsic adsorption kinetics. The model is verified using protein gradient elution data. Simulations establish that typical symptoms of denaturation in frontal and elution chromatogrrams include sensitivity to changes in feed composition, column length, particle size, and operating conditions (feed size, flow rate, and column history). When a denatured species adsorbs irreversibly, the elution chromatogram shows decreasing peak area with increasing incubation time and apparent adsorption hysteresis over repeated cycles. In gradient elution, the peak elution order, resolution, and relative peak height depend highly on modulator properties and operating conditions. Interfering species limit solid-phase induced denaturation by competing for binding sites. Strategies for detecting and minimizing denaturation are proposed.
    Additional Material: 12 Ill.
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  • 111
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1087-1087 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 112
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1087-1088 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 113
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 114
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1117-1117 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 115
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1105-1117 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pressure drops, gas holdup, and mass-transfer coefficients were measured in two concentric-tube airlift reactors of 30 and 300 L (nominal volume). The aspect ratio and the ratio of riser to downcomer cross section were the same for both reactors, but the geometry of the gas separation section was different. The influence of the bottom and top clearances was studied using water and carboxymethyl cellulose solutions and covering a range of effective viscosity from 10-3 to 25 × 10-3 Pa·s. The pressure drop results expressed as a Euler number were satisfactorily correlated with Fr, Ga, and a bubble disengagement group M. Correlations are presented also for the gas holdup in the riser, downcomer, and gas separator. The last-mentioned coincides with the correlation for the total holdup in the reactor. The gas-liquid mass-transfer coefficients for all the liquids and geometric variables in both reactors were successfully correlated as Sherwood numbers.
    Additional Material: 13 Ill.
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  • 116
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1156-1166 
    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 Semibatch gas-liquid reactor model based on a lumped kinetic schem for the liquid-phase oxidation of p-xylene to p-toluic acid catalyzed by cobalt naphtenate is developed. The model accounts for the complex nature of the involved reaction network, as well as for the interphase and intraphase mass transport processes of both reactants and products. The model reliability is tested by comparison with suitable experimental data obtained in a semibatch oxidation reactor, where the role of the composition of both the gaseous and the liquid feed has been investigated. It is shown that the model describes the reactor behavior in any of the regimes which may prevail depending upon the operating conditions and the depletion of liquid reactants in time.
    Additional Material: 9 Ill.
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  • 117
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 378-379 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 118
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 381-382 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 119
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 120
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 385-394 
    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 methods are presented for calculating the interfacial tension between two immiscible Newtonian fluids. The procedures require only two measurements of the approximate interface shape during the low-Reynold-number interfacial-tension-driven transient motion of (i) the relaxation of a modestly elongated drop back to a spherical shape or (ii) the growth of capillary wave instabilities along the surface of a thread. The interfacial tension can be estimated by comparing the time differences between the two experimental measurements with tabulated and numerically generated results for the approximate shape evolution. The numerical results are generated using boundary integral method for similar model free-boundary problems at low Reynolds numbers. The tabulated results are presented for drop to suspending fluid viscosity ratios 0.01 to 10.
    Additional Material: 9 Ill.
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  • 121
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 122
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1412-1417 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 6 Ill.
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  • 123
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1426-1430 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 124
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1422-1425 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 125
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1418-1421 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 126
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 127
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1433-1439 
    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 generally believed that oil samples heat faster in a microwave oven than do water samples of the same mass. For sufficiently large and thich samples this conventional wisdom is indeed correct, but this trend can be far from true in smaller samples. In a commercially-made home microwave oven, we observed that with decreasing sample size the heating rate of a water sample increases much faster than that of an oil sample. At 50 g the heating rate of a water sample is several times greater than that of an oil sample. Additionally, in studies of cylindrical samples in a customized oven having a unidirectional microwave source, the heating rate of water samples smaller than 2.4 cm in radius is greater than that of oil samples and is a strongly oscillatory increasing function of decreasing sample radius. Combining Maxwell's theory of microwave penetration and the heat conduction equation, we show that this previously unreported oscillatory heating behavior results from the added power absorbed by samples due to resonant absorption of microwaves. The added power arises from standing waves produced by internally reflected microwaves. This effect is small for oil because only 3% of the microwave power is reflected at an oil-air interface. On the other hand, 64% is reflected at a water-air interface, which causes strong resonant heating. Our findings might prove to be useful for future consumer food product development or oven design.
    Additional Material: 6 Ill.
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  • 128
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1466-1478 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: As recently recognized, distillation columns, operating with reflux and boilup as independent inputs, may have multiple steady-state solutions, even in the ideal binary case. Two fundamentally different sources may cause the multiplicity, and in both cases some operating points are found to be unstable. This article provides evidence for the instability and discusses the effect of operating conditions on stability. Increasing the internal flow rates increases the probability of instability; when flows other than reflux and boilup are used as independent inputs, an operating point may become unstable if the level control is not sufficiently tight. In this case, a limit cycle, usually stable, appears as the steady state goes unstable.
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  • 129
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    AIChE Journal 40 (1994), S. 1479-1487 
    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 mixed integer nonlinear programming (MINLP) model is presented for synthesizing reactive distillation columns when chemical reaction equilibrium cannot be assured. The MINLP minimizes the total annual cost subject to a rigorous tray-by-tray model. The solution of this MINLP yields the optimal number of trays, the optimal feed rates, and the optimal feed tray locations. The liquid holdup per tray, the reflux ratio, and the temperature and composition profiles within the column are optimized as well. The MINLP is solved using generalized Benders decomposition, and the technique is illustrated with ethylene glycol synthesis.
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  • 130
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1549-1557 
    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 “capillary condensation” in liquid phase was analyzed theoretically and experimentally, in which a solute in solvent could be separated out as a liquid into small pores by capillary effect. The “liquid-phase capillary condensation” is defined as capillary phase separation. The separated phase is counted as “adsorbed” amount on porous materials. The relation between the concentration and a critical radius of the phase separation was derived. A new method to estimate liquid-phase adsorption isotherms of adsorbates with limited solubility from pore-size distribution of solids is based on this concept. The amount absorbed consists of the separated phase and adsorption on surface expressed with a single parameter. While the surface adsorption alone could not explain measured isotherms, this model showed good agreements between experimental and estimated isotherms for adsorption of four kinds of aromatic compounds from aqueous solution onto three categories of porous solids to demonstrate the significance of the capillary phase separation. The applicability of the method to solid solutes is also discussed.
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  • 131
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    AIChE Journal 40 (1994), S. 1574-1579 
    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 relatively simple continuous dilution method with on-line spectrophotometric measurement has been used to determine the phase transition boundaries of aqueous two-phase polymer systems. The observed range of compositions over which the phase transition occurs is dominated by the polydispersity of the polymers, but also is a function of the dilution path followed. The binodal curve obtained by the continuous dilution method agrees well with the results obtained by the traditional method of phase equilibration, separation and analysis of liquid chromatography, which is slower and requires more expensive equipment.
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  • 132
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    AIChE Journal 40 (1994), S. 1669-1684 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In heterogenous olefin polymerization with Ziegler catalysts, the influence of monomer mass transport in the growing granule on polymer properties has been extensively modeled, but it has not been possible to clearly establish the importance of diffusion experimentally since the multisited nature of most Ziegler catalysts can produce similar effects. In this study, ethylene-propylene copolymers were made with single-sited metallocene catalysts by slurry polymerization in liquid monomers. These copolymers had a relatively narrow molecular weight distribution with a composition distribution (CD) broader than expected for a single-site catalyst. Data analysis indicates that mass-transfer limitations in the polymer particles are the most likely explanation for the observed results. For amorphous copolymers, a diffusion/reaction model could predict CD breadth in good agreement with experimental data, but for semicrystalline polymers the model was inaccurate. We postulate that model inadequacies are due to radial gradients in monomer diffusivity during polymerization which the model does not account for.
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  • 133
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    AIChE Journal 40 (1994) 
    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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  • 134
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    AIChE Journal 40 (1994), S. 1782-1793 
    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 article investigates the effect of shear-thinning viscosity on chaotic mixing when the kinematics first begin to deviate from Newtonian flow. Computations are done for a 2-D, time-periodic flow between eccentric cylinders. The effectiveness of mixing is analyzed by examining the asymptotic coverage of a passive tracer, character and location of periodic points, and the rate of stretching of fluid elements. Small variations in the velocity field associated with non-Newtonian kinematics produce large effects in the chaotic advection of a passive tracer. The stretching rate remains exponential, but with a long time constant as the shear-thinning effect increases, often resulting in the birth of new periodic islands and a decrease in the asymptotic coverage of the tracer. Exceptions to these observations are possible: both the stretching rate and the asymptotic coverage might increase as shear thinning increases. Results also indicate that suitable manipulation of operating conditions can produce shear-thinning flows which mix as well as Newtonian flows. Since significant effects are observed with less than a 4% difference in the velocity fields, the assumption of Newtonian kinematics can lead to large errors in the design and operation of process mixing equipment for non-Newtonian fluids.
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  • 135
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    AIChE Journal 40 (1994), S. 1794-1803 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Time-dependent viscous flows driven by capillarity act to minimize the surface area of a fluid bounded in a plane geometry with initial gradients in surface curvature. These free-surface flows are solved by a finite-element model applied to describe the viscous sintering of two-dimensional ceramic particles. The numerical model is validated by comparison to the analytical solution obtained by Hopper (1990) for the coalescence of two infinite cylinders of equal cross section and is applied to several other geometries pertinent to the study of particle sintering for which analytical results are not available. Details of the flow fields and morphological evolution lend insight to the physical behavior of these systems and provide a basis for the more complete understanding of viscous sintering phenomena.
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  • 136
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    AIChE Journal 40 (1994), S. 1924-1925 
    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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  • 137
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    AIChE Journal 40 (1994), S. 1926-1926 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 138
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    AIChE Journal 40 (1994) 
    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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  • 139
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    AIChE Journal 40 (1994), S. 269-282 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new comprehensive real-time identification/control methodology based on the concept of nonlinear autoregressive exogenous input (NARX) models and adaptive, nonlinear, model-predictive control (ANMPC) is applied to a pH neutralization process. The existing NARX model theory has been extended by incorporating measured disturbances. NARX models have shown superior predictive characteristics in comparison to linear models. The proposed real-time methodology uses a pointer vector being created during an initial identification and model structure selection procedure. Using this pointer vector, which allocates the chosen elements from the pool of all possible linear and nonlinear combinations, one needs no explicit information about the model structure for the closed-loop control. The nonlinear programming problem encountered in ANMPC is solved by a gradient-based modified Marquardt and finite difference methods. The design procedure and explicit algorithms are discussed for the multiinput/multioutput case. A pH wastewater neutralization process used illustrates and verifies the procedure by computer simulations and a real-time laboratory-scale experiments.
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  • 140
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    AIChE Journal 40 (1994), S. 321-333 
    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 has been developed to predict the coupled hydrodynamics and high-molecular-weight protein transport in mammalian-cell hollow-fiber bioreactors (HFBRs). The analysis applies to reactors with isotropic ultrafiltration membranes under startup conditions when the extracapillary space (ECS) is essentially unobstructed by cells. The model confirms the experimental finding that secondary ECS flows, engendered by the primary flow in the fiber lumens, can cause significant downstream polarization of ECS proteins at typical mammalian-cell HFBR operating conditions. It also reveals that the osmotic activity of the proteins, by curtailing transmembrane fluid fluxes, can influence strongly the outcome of the polarization process. In fact, at order-of-magnitude higher protein concentrations and/or lower recycle flow rates, the secondary flow velocities can be reduced by as much as six orders-of-magnitude throughout the ECS, thereby virtually eliminating the polarization problem. This result has important implications for improved reactor startup procedures.
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  • 141
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    AIChE Journal 40 (1994), S. 1976-1982 
    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 200-s PSA cycle involving both pressure equalization and product backfill steps has been experimentally studied on a four-bed system, where LINDE 5 A zeolites were used as the adsorbent to separate oxygen from air. This cycle is operated under a pressure ratio of 4.3. During the experiment, the pressure history and flow rates, as well as the concentration of the product stream have been continuously monitored. This is the first time detailed experimental data on a four-bed system are presented. Under favorable conditions, this system produces better than 90% oxygen at a recovery of 17%. For the low-pressure ratio, such a recovery could not have been achieved without the pressure equalization step and the reduced purge operation. Recovery and throughput, however, are not as high as one would expect from a linear local equilibrium model. The self-broadening effect of the purge wave has been identified as the major cause of underperformance.
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  • 142
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    AIChE Journal 40 (1994), S. 369-372 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 143
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    AIChE Journal 40 (1994), S. 380-381 
    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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  • 144
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    AIChE Journal 40 (1994), S. 395-406 
    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 substantial effort has been made by numerous investigators to describe droplet breakage and coalescence in turbulent dispersions. An attempt is made here to improve these models based on existing frameworks and recent advances described in the literature. Two-step mechanisms are considered for both the breakage and coalescence models. The drop breakage function is structured as the product of the drop-eddy collision frequency and breakage efficiency which reflect the energetics of turbulent liquid-liquid dispersions. The coalescence function retains the former structure of the product of drop-drop collision frequency and coalescence efficiency. The coalescence efficiency model has been modified to account for the effects of film drainage for drops with partially mobile interfaces. These models overcome several inconsistencies observed in previous efforts and are applicable for dense dispersions (about φ[0.10-0.30]). For the daughter drops produced by breakage, a probability density is proposed based on the energy requirements for the formation of daughter drops.
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  • 145
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    AIChE Journal 40 (1994), S. 419-423 
    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-dimensional Stokes flow through a thin screen which has a regular array of holes with two orthogonal axes of symmetry has been studied. The governing equation is simplified by the Roscoe potential and solved by an efficient eigenfunction expansion and collocation method. The resistance is found for circular and square holes in square arrays, and circular and hexagonal holes in triangular arrays.
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  • 146
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    AIChE Journal 40 (1994), S. 424-432 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mixing effects are evaluated for double jet semibatch and continuous stirred precipitators by a model which gives the variation of the primary nucleation flux from the mixing conditions. The predicted trends are compared with results of various authors, including those from a new study of calcium oxalate semibatch double-jet precipitation. Satisfactory qualitative agreement is found for the different chemical systems as a function of feed rate, stirring speed and feed locations for calcium oxalate precipitation. Two types of precipitation systems are demonstrated, depending on the ratio added/tank volume, the initial supersaturations and the intrinsic stiffness factor of a given precipitation. The difference between the two types depends on the increase or reduction of the primary nucleation flux by imperfect mixing with respect to the reference primary nucleation flux obtained with perfect mixing.
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  • 147
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    AIChE Journal 40 (1994), S. 445-462 
    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 weight distribution (MWD) estimator for batch methyl methacrylate solution polymerization is implemented experimentally for on-line control and estimation of the MWD. The estimator is based on an extended Kalman filter and provides current estimates of the entire MWD, reaction temperature, monomer conversion, and initiator conversion. It uses a detailed polymerization model, on-line monomer conversion measurements, temperature measurements, and periodic, time-delayed measurements of the MWD from an on-line size-exclusion chromatograph. The estimator is shown to perform well with several on-line MWD estimation experiments. Real-time feedback control of the molecular weight is presented by utilizing the on-line MWD information. Temperature, monomer-addition, and simultaneous temperature and monomer-addition control are investigated experimentally to achieve a specific constant weight-average molecular weight. The on-line feedback control is effective in rejecting realistic disturbances which deteriorate molecular weight control.
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  • 148
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    AIChE Journal 40 (1994), S. 473-495 
    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 the synthesis of discrete-time feedforward/feedback control systems for general nonlinear processes with stable zero dynamics. Depending on the process under consideration, the derived feedforward/feedback controllers can completely eliminate the effect of measurable disturbances and produce a prespecified linear response with respect to a reference input, or provide integral-square error optimal response to step changes in the disturbances and a prespecified linear response with respect to a reference input. In either case, the developed feedforward/feedback controllers allow for the asymptotic rejection of unmeasurable disturbances. These controllers are derived within the globally linearizing control frame-work, first under full state information and then in the absence of state measurements. The internal stability of the closed-loop system is addressed. The derived controllers are interpreted from a model-predictive point of view, and their connections with the feedforward internal model control and the model algorithmic control are established. The theoretical results are illustrated through a continuous stirred-tank reactor example.
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  • 149
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    AIChE Journal 40 (1994), S. 506-520 
    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 olefin polymerization processes produce a wide range of resin grades to suit market demand. Determining the transition policy between these grades is an important consideration that can affect process economics and safety. In this article, we compare several grade transition strategies and the relative performance of solution, slurry, bulk and gas-phase processes for the production of polypropylene, linear low-density polyethylene, high-density polyethylene and ethylene-propylene rubber. It is shown that the most important parameters that determine the grade transition performance of a process are reactor design, residence time, runtime per grade and residence time distribution of the polymer, gas and/or solution phases. Slow hydrogen dynamics severely retard grade changes involving increases in product molecular weight. The simulation results are obtained by using the dynamic simulation package “POLYRED” developed at the University of Wisconsin-Madison.
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  • 150
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    AIChE Journal 40 (1994), S. 670-675 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Vented extruder devolatilization (DV) of PS melt containing 6,000 ppm styrene was studied by scanning electron microscopy (SEM) and video photography. Vacuum DV of a polymer is accompanied by foaming, which starts instantaneously upon supersaturation of the stretched melt and is enhanced at higher speeds of the vented extruder screw. As the volatiles are removed from the melt, foaming gradually ceases, starting with the pushing flight of the screw. The experimental installation design allowed us to quench the polymer melt in the DV zone at various stages of the process. Samples taken from four areas of the channel width were investigated by SEM. Bubble nucleation in the melt appears to take place mainly in the border area adjoining the gas phase. In the shear field caused by screw rotation, large bubbles become noticeably elongated. Their surface, as well as the free surface of the melt, is covered with blisters, 1-100 μm in size. Microblisters are often concentrated in areas subjected to stretching. Calculations of cooling due to volatile evaporation and of heating due to viscous dissipation near a growing bubble shows that the process of foam-enhanced DV of a PS/styrene system can be regarded isothermal if the initial volatile concentration does not exceed approximately 1%.
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  • 151
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    AIChE Journal 40 (1994), S. 692-703 
    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 adhesion of biological cells to substrates is often mediated by binding between cellular receptors and substrate-bound ligand. In this work, we used a centrifugation assay to measure the adhesion of rat basophilic leukemia (RBL) cells coated with immunoglobulin E (IgE) to substrates coated with the ligand dinitrophenol (DNP). Increasing force, decreasing DNP substrate density, and decreasing cell surface IgE density all led to decreasing adhesion. Experiments performed at low IgE cell surface densities, in which few tethers from between cell and substrate suggest individual tethers have a binding strength of 2 to 4 microdyne, in agreement with previous measurements of the force to uproot receptors from the plasma membrane. We use this system to show how subpopulations expressing different numbers of cell surface receptors may be separated by exploiting their differential adhesiveness to substrates.
    Additional Material: 7 Ill.
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  • 152
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    AIChE Journal 40 (1994), S. 1488-1497 
    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 dynamic optimization technique presented combines a neural network model with a universal dynamic matrix control (UDMC) algorithm. This technique utilizes a nonlinear-model-predictive control technique for on-line optimization and feedback control by using a dynamic neural net model. This approach offers two important advantages over conventional UDMC. One is that a dynamic neural net model can be developed from process data and used for optimization calculations, thus achieving optimization without a first principle model. This neural-network-based optimization approach also produces good performance even with processmodel mismatch. The other is that our neural-net-model-based UDMC algorithm greatly reduces the computation time required for the nonlinear dynamic matrix used for the successive quadratic programming algorithm. The development of this technique also involved an analysis of the effect of network structure on dynamic optimization. A state-space-based neural network model which utilizes a priori process knowledge is best suited for optimization calculations. Advantages of this technique are illustrated by simulation for two chemical processes.
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  • 153
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    AIChE Journal 40 (1994), S. 1515-1523 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Four different coals were instantaneously introduced into a laboratory-scale pyrolysis chamber at various temperatures, and their develatilization profiles were analyzed with respect to kinetics. The experimental setup consisted of a gas chromatograph (GC) with a pyrolysis unit, an empty column, and a detector. Detector signals were digitalized and stored for further handling. Normally, 1,024 values were sampled at 250 Hz. For deconvolving the true instantaneous devolatilization from the observed detector response, the residence time distribution was compensated for.An empirical model approach is developed to correlate the total devolatilization rates when instantaneously introducing a particle in a constant temperature environment. The model is also extended to pyrolysis application.
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  • 154
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    AIChE Journal 40 (1994), S. 1535-1548 
    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 counterflow jet reactor has been designed to study the purely homogeneous kinetics of endothermic reactions. The reactor consists of two vertical, coaxial, counterflowing, laminar jets and radial-flow exit region. It can be used to generate a reaction zone near the stagnation point and away from walls, thus eliminating the possibility of surface reactions. One jet is heated and contains only a suitable carrier gas such as hydrogen and nitrogen, while the other is unheated and contains the compound(s) under study diluted in the same carrier gas. A 2-D model of the process has been used to simulate the thermal decomposition of tertiary-butyl-arsine, a precursor for metal-organic chemical vapor deposition of GaAs films. Performance diagrams based on Reynolds and Demköhler numbers were constructed to identify optimal operating conditions and to demonstrate the feasibility of the technique. This reactor appears to be an attractive choice for studies of the purely homogeneous kinetics of endothermic reactions at pressures close to atmospheric.
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  • 155
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    AIChE Journal 40 (1994), S. 1558-1573 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A general molecular-based formalism developed rigorously establishes microscopic bases of the supercritical solubility enhancement in terms of well-defined molecular correlation function integrals by unambiguously splitting the mixture's properties into short-(finite) and long-range (diverging) contributions. Consequently, the short-range nature of the solute's and solvent's residual chemical potentials is proved and the change of the solvent's local environment around an infinitely dilute solute and its finite contribution to solute mechanical partial molar properties are interpreted in terms of the short-range solute-solvent and solvent-solvent direct correlation function integrals. The solute-induced effect on the system's microstructure and thermodynamics approaches zero as the mixture approaches ideality or the solute becomes an ideal gas particle. At the solvent's critical conditions, the solute-induced effect on the solute's partial molar properties shows no compressibility-driven singularity, though along the critical isotherm it can exhibit a finite extremum or a change of curvature near critical density, depending on the type and strength of solute-solvent interactions. The utility of the proposed solvation formalism is illustrated using statistical mechanical integral equation calculations for three simple models of infinitely dilute near-critical mixtures: pyrene-CO2, diterbutyl nitroxide-ethane, and Ne-Xe.
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  • 156
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    AIChE Journal 40 (1994) 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 157
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    AIChE Journal 40 (1994), S. 1580-1593 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: General procedures are outlined for the simulation and propagation of random and systematic errors in thermophysical property experiments. Density second virial coefficients B(T) from sonic velocity and Joule-Thomson (J-T) experiments are examined for error propagation where the connecting thermodynamic identity is a differential equation with missing boundary conditions. A recent controversy is addressed concerning B(T) at subcritical temperatures for pure hydrocarbon gases from direct density measurements vs. new sonic velocity data. Sonic velocity results are more likely correct with adsorption errors causing the problem in the density measurements.Two new model consistency tests are developed for checking assumed temperature models in the reduction of sonic velocity and J-T data to B(T). Excellent values of B(T) are then obtained from either type of data when the original experiments are free of errors. Random errors propagate systematically when the connecting equation is a differential equation. Sonic data must be of high precision (± 10 ppm) to generate B(T) to ±1 cm3/mol due to complications in data reduction arising from the temperature model/random error interaction. Except perhaps for adsorption errors, systematic errors in the sonic velocities are unimportant to B(T). J-T data provide propagation factors near unity with errors in B(T) higher at higher temperature, unlike sonic velocities.
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  • 158
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    AIChE Journal 40 (1994), S. 1611-1617 
    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 capillary jet of liquid impinges on a planar surface that is normally oriented to the axis of the jet. The surface is initially covered with a thin uniform film of a viscous liquid. The impact and radial spreading of the liquid from the jet cause the underlying viscous film to be removed from the surface. An approximate analysis predicts the thinning rate of the film in the stagnation region of the jet. It uses the shear stress and pressure distribution of the classical Homann flow as boundary conditions for an analytical solution of the Reynolds lubrication equations in this underlying viscous film. A more exact analysis modifies the Homann flow to account for the mobility of the liquid film beneath the spreading jet and sheds light on the limitations of the analytical lubrication analysis. Data presented are in excellent agreement with the theory, subject only to the choice of a value for the hydrodynamic constant that appears in the Homann analysis.
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  • 159
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    AIChE Journal 40 (1994), S. 1629-1638 
    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 physical absorption of CO2 and propene into toluene/water emulsions is studied in a stirred cell and laminar film absorber. Experimentally observed masstransfer rates are compared to an absorption model, based on Higbie's penetration theory describing physical gas absorption into an emulsion. For all absorption experiments in a stirred cell absorber (toluene fractions and stirring rates), experimentally observed mass-transfer rates are considerably higher than the rates predicted by the absorption model. Moreover, the absorption rate decreases with increasing stirring rate, whereas no influence of the stirring rate is predicted by the absorption model. In contradiction to the absorption experiments in a stirred cell absorber, the observed mass-transfer rates in the laminar film absorber agree with the model simulations. Probable existence of a very thin toluene layer is observed on top of the emulsion for the stirred cell experiments, likely due to minor phase separation. Since in the laminar film absorber gas-liquid interface and the gravity force are parallel, this phenomenon does not probably occur significantly for absorption experiments in this absorber. The observed mass-transfer phenomena can be explained, at least qualitatively, from the occurrence of a thin toluene layer.
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  • 160
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    AIChE Journal 40 (1994), S. 1193-1202 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Sol-gel techniques have shown great potential for producing ceramic materials of designed composition and properties. A typical sol-gel process involves the hydrolysis and polymerization of one or more metal alkoxides in an alcohol solution in a batch reactor to form a homogeneous gel, which is then further treated to provide the type of ceramic desired (such as aerogel, glass, crystal, and coating). Several authors have suggested that diffusion effects may influence the development of the gel microstructure. We investigate what governs the diffusivity of the precursors using the pulsed-gradient-spin-echo NMR technique. This initial report focuses on the early stages of the batch reaction.The system chosen is the acid catalyzed hydrolysis and condensation of tetraethyl orthosilicated in ethanol. 1H PGSE NMR and 29Si NMR show that the diffusivities of the silicate precursors are strong functions both of the molecular weight and of hydrogen bonding between the polar functional groups and the solvent. Moreover, since hydrolysis increases and polymerization reduces the concentration of these polar groups, the mobility of the reactive oligomers changes in a complex manner. Combining our results from PGSE NMR and gas chromatography, we estimate the extent of hydrogen bonding effect on the mobility of various oligomers, providing a model to predict diffusivity trends throughout the batch reaction.
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  • 161
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    AIChE Journal 40 (1994), S. 2034-2044 
    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 parallel transport of a protein by surface and pore diffusion within a highly porous ion exchanger is studied by measuring equilibria and uptake curves for adsorption of bovine serum albumin (BSA) on two different strongly basic chitosan ion exchangers (hard gels): Ch-2503 and Ch-2507 at pH 6.9 and 298 K. Experimental equilibrium isotherms are correlated by the Langmuir equation. Intraparticle effective diffusivities of BSA (Deff) are determined from the homogeneous Fickian diffusion model, increasing with the bulk phase concentration increase of BSA (C0). It suggests the existence of parallel diffusion. The surface diffusivity DS for the parallel diffusion model is determined from the Deff, and DS = 0.47 × 10-13 m2 · s-1 (Ch-2507) and 2.4 × 10-13 m2 · s-1 (Ch-2503) were obtained. Pore diffusivities based on the pore diffusion control (D′P) are obtained by matching the shrinking core model with the experimental uptake curves. D′P decreases with increasing C0. Since D′P in Ch-2507 is constant when C0 ≥ 1 kg·m-3, the constant value 2.7 × 10-11 m2 · s-1 is taken as the accurate pore diffusivity (DP). As D′P in Ch-2503 does not approach a constant value, DP = 1.0 × 10-11 m2 · s-1 is determined by matching the parallel diffusion model with the uptake data, and the model calculated using experimental values of DS and DP agrees reasonably well with the uptake data for Ch-2507 and Ch-2503. This theoretical approach may be applied not only for intraparticle diffusion of proteins but any adsorbates in porous materials.
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    AIChE Journal 40 (1994), S. 365-368 
    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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  • 163
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    AIChE Journal 40 (1994), S. 1018-1025 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Emission of carbon monoxide (CO), formaldehyde (CH2O), and unburned methane (CH4) are calculated for premixed methane/air mixtures impinging on a flat surface as functions of surface temperature, equivalence ratio, and strain rate with detailed chemistry involving 46 reversible reactions and 16 species using numerical bifurcation theory. Multiple solutions with different selectivities to stable products are found. On the extinguished branch unburned CH4, molecular hydrogen (H2), CO, and CH2O dominate, whereas on the ignited branch carbon dioxide (CO2) predominates near the surface. Cold walls can promote the selectivity to CO and CH2O near extinction, and high flow rates can increase considerably the formation of CO, CH2O, and unburned CH4. For example, an ignited stoichiometric methane/air mixture (9.5% CH4 in air) impinging on a surface of 1,000 K is calculated to produce 2% CO, 150 ppm CH2O, and 3% unburned CH4 for a strain rate of 500 s-1. Maximum efficiency of CH4 and minimum selectivity to CH2O occur near the stoichiometric ratio, whereas minimum selectivity to CO occurs for fuel lean mixtures. Comparison of combustion near surfaces with freely propagating flames is also shown.
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  • 164
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    AIChE Journal 40 (1994), S. 187-192 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 165
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    AIChE Journal 40 (1994) 
    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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  • 166
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    AIChE Journal 40 (1994), S. 207-214 
    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 interactive effects of heat and mass transfer in evaporation of binary mixtures flowing as falling films on vertical surfaces was investigated. Evaporative heat-transfer coefficients were measured for aqueous mixtures of ethylene and propylene glycol, with boiling ranges up to 55°C. Tests were carried out at atmospheric pressure with heat fluxes ranging from 3,000 to 25,000 W/m2, and film Reynolds numbers ranging from 300 to 3,000. Results indicated that the heat-transfer coefficient for mixtures depends weakly on wall superheat and film Reynolds number, but strongly depends on mixture composition. Analysis of the results indicates that mass-transfer resistance in the liquid film causes significant elevation of the interface temperature, causing a reduction of the effective temperature driving force. A semiempirical model for correlation of the interactive heat-and mass-transfer phenomena is proposed.
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  • 167
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    AIChE Journal 40 (1994), S. 229-242 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dynamic wetting speeds are limited by the gross entrainment of air between the liquid and the moving substrate. We present experimental data for the curtaincoating method, in which liquid impinges at high speed on the substrate. We also show that air entrainment is strongly affected by macroscopic hydrodynamics and is subject to hysteresis. Using boundary-layer theory, a simple hydrodynamic model is developed for the flow field in the impingement zone away from the dynamic wetting line. The model approximately accounts for the shear thinning of polymer solutions and for the influence of surface tension. We apply the molecular kinetic theory of dynamic wetting, modified to account for hydrodynamic stress, to the immediate vicinity of the wetting line. The main result is a correlation for airentrainment data.The experimentally calibrated model predicts that the hydrodynamic assist of wetting is greatest when the dynamic wetting line is located beneath the impinging curtain. Flow visualization supports this physical picture.
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  • 168
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    AIChE Journal 40 (1994), S. 193-206 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A systematic study conducted explores the hydrodynamics of a circulating fluidized bed with polymeric particles employing polyethylene resins with a particle density of 660 kg/m3 and size ranging from 90 to 500 μm. The study indicates that polyethylene resins can be fluidized smoothly in the fast fluidization regime. However, the operating range of the fast fluidization regime for these particles is smaller than that for FCC particles. The deviation of the fluidization behavior of polyethylene particles from that of common Group-A particles is explained considering the interparticle forces. Experiments with fine polyethylene particles are also conducted with coarse particles added in a circulating fluidized bed. Axial profiles of solid holdups in a bed with and without coarse particles, as well as overall fine particle holdup, are studied. The results show a significantly wider operating range of the fast fluidization regime and enhancement of fine particle holdups in a bed with the presence of coarse particles. For comparison, fluidization with FCC particles is also conducted. A mechanistic model considering particle-particle collision is proposed. The model accounts for the momentum exchange rate between a coarse particle and a cloud of fine particles, which explains the enhancement of fine particle holdups observed experimentally.
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  • 169
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    AIChE Journal 40 (1994), S. 283-293 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Using Brownian dynamics, equilibrium and dynamic properties are calculated for colloidal suspensions that are stabilized throug the Milner, Witten and Cates (1988) steric potential. Results are reported for osmotic pressure, radial distribution functions, static structure factors, and self-diffusion coefficients. The sterically-stabilized systems are also approximated by equivalent hard spheres, with good agreement for osmotic pressure and long-range structure. The suitability of the potential to model the behavior of a real system is explored by comparing static structure factors calculated from Brownian dynamics simulations to those measured using SANS (Markovic et al., 1986). Finally, the effects of Hamaker and hydrodynamic forces on calculated properties are investigated.
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  • 170
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    AIChE Journal 40 (1994), S. 294-311 
    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 kinetic model of free-radical surface graft polymerization developed is based on a conservational polymerization and molecular-weight distribution (CPMWD) numerical algorithm. The CPMWD model uses an implicit numerical technique to solve for the coupled monomer, surface site, and total growing polymer differential rate equations, which ensure that conservation of mass is maintained. The model formulation allows for the incorporation of kinetic rate coefficients, which are a function of the chain length of the reacting species, the solution viscosity, and the concentration of surface grafted polymer. The model also makes it possible to evaluate the monomer conversion, the graft yield and the molecular weight distributions of the homopolymer and surface-grafted polymer for the complete duration of the graft polymerization reaction. Its application was demonstrated for a model system of vinylpyrrolidone graft polymerization onto the surface of a silica substrate.
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  • 171
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    AIChE Journal 40 (1994), S. 361-364 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Various phenolic compounds in aqueous buffer solutions were contacted batchwise with powdered activated carbon. Relatively slow, but continual, decreases in the solution phenolic concentrations were measured over a period of several weeks. The decreases were due to oxidative coupling reactions of the phenolics which occurred on the carbon surface subsequent to adsorption. The effects of time, pH, dissolved oxygen, and the molecular nature of the phenolic were determined.
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  • 172
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    AIChE Journal 40 (1994), S. 1440-1448 
    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 forced convective heat and mass transfer to spherical-cap bubbles were investigated analytically. Potential flow was assumed outside the bubble except at the bubble surface where the boundary layer approximation was adopted. The present analytical study produced the following exact solution: \documentclass{article}\pagestyle{empty}\begin{document}$$ Nu = 2.113{\rm}\left({Pe} \right)^{1/2} $$\end{document} for the average Nusselt number where Pe is the Peclet number. The derived equation was compared with the available experimental mass-transfer results.
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  • 173
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    AIChE Journal 40 (1994), S. 1449-1458 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Gel/micelle materials, comprising hydrogels containing block copolymer micelles, have the potential to be very useful in a variety of extraction and controlled release applications. It is demonstrated that block copolymer surfactants can be immobilized in calcium alginate gels and that the resulting composite material preferentially solubilizes the model hydrophobic solute naphthalene. Five different polyethylene oxide-polyropylene oxide-polyethylene oxide triblock copolymer surfactants are considered, and the qualitatively different properties exhibited are interpreted in light of the properties of these surfactants in solution. Alginate gel concentrations of 22.5 and 52.5 g/L and surfactant concentrations ranging from 20.4 to 136 g/L are considered. The data indicate that micelles can be permanently immobilized for purposes of extraction or controlled release and that the extent of solute uptake or release can be altered by varying gel and surfactant concentration and the type of surfactant employed.
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  • 174
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    AIChE Journal 40 (1994), S. 1459-1465 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experimental studies were performed to assess the effect of salt addition on the extraction of 1-butanol, ethanol and acetone from dilute aqueous solutions using cyclopentanol, n-valeraldehyde, tert-amyl alcohol, and Adol 85NF as extractants. The liquid-liquid partitioning was examined for a few strong electrolytes in a broad range of concentrations. Results demonstrate that the distribution coefficient and selectivity in systems with reduced water activity resulting from salt addition were markedly increased. These observations can be qualitatively explained on the basis of the hydration theory. It was also determined that strong electrolytes added to the aqueous feed reduced extractant solubility in the aqueous phase, thus contributing to lower solvent losses. The results showed that the extraction efficiency was not significantly affected by increasing salt content beyond a level that reduces the water activity to a value of 0.92.
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  • 175
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    AIChE Journal 40 (1994), S. 1498-1514 
    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 mathematical tools necessary to describe quantitatively the chemical processes that dictate the performance of exhaust oxygen sensors are developed. Such sensors are used commonly to monitor exhaust streams generated by internal-combustion processes. Calculated results compare well with available experimental results, although several open questions are idetified that require more experimental data. The mathematical formalism for describing the transport of gaseous species through the porous spinel structure protecting the platinum electrode on the exhaust side of the sensor is developed based on the Stefan-Maxwell equations. The kinetic processes occurring at the interface formed by the platinum electrode and the spinel structure, including the oxidation of hydrogen and carbon monoxide and various adsorption-desorption reactions, enter as boundary conditions for the transport equations. The analysis enables one to calculate the sensor's voltage response as a function of the air-to-fuel ratio λ and to investigate phenomena such as the magnitude of the voltage jump in going from rich to lean gas mixtures and the λ value at which this jump occurs.
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  • 176
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    AIChE Journal 40 (1994), S. 1594-1598 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 177
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    AIChE Journal 40 (1994), S. 1601-1610 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effect of imposed large-amplitude oscillations on turbulent drag is studied. The system consists of water flow through a straight 5.08-cm pipe. The velocity gradient at the wall is measured with flush-mounted electrochemical mass-transfer probes. Newly developed numerical algorithms are used to analyze the probe performance in the presence of unsteady flows. Sinusoidal oscillations are at large enough frequencies, ω+ = 0.0138-0.0506, that a pseudo-steady-state approximation cannot be made. The ratio of the time-averaged velocity gradient at the wall, with and without oscillations, S̄, varies between 1.00 and 1.03, provided flow reversal does not occur. However, two experiments in which reversed flows existed at the wall for an appreciable period of time show drag reductions of 7 and 13%.Imposed nonsinusoidal oscillations are also studied for a period of favorable pressure gradient, about twice longer than that of unfavorable, and two sudden changes in the pressure gradient. Experiments at Re = 9,700 with T0 of 2.00, 2.45, and 3.46 s, and at Re = 19,200 with T0 = 3.46 give values of S̄ = 1.04-1.08. At Re = 19,200 and T0 = 2.00, 1.50, 1.00 s, drag reductions are 10-15%. This phenomenon could be associated with the speed with which a flow adjusts to sudden changes in the pressure gradient.
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  • 178
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    AIChE Journal 40 (1994), S. 1618-1628 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Separating mixtures of α-amino butyric acid (ABA) and isoleucine (Ile) by displacement chromatography with a cation exchange resin and an alkaline displacer leads to the formation of a displacement train, in which only ABA is recovered as a pure component, while Ile is recovered in a mixed band with ABA. The purity of the Ile band depends on the concentration of the displacer, and essentially pure Ile is obtained when the displacer concentration is reduced to a low value. The observed behavior is explained by considering the nonideality of the equilibrium uptake of these amino acids by the resin. An equilibrium model, representing the pure component isotherms, predicts variable selectivity and the occurrence of selectivity reversal in the two-component system. Analyses using this model based on the theory of coherent waves and a numerical solution of the conservation equations for the displacement chromatography process agree with the observed behavior, predicting the formation of “azeotropic” bands during the development of the displacement train. Such analyses are used to determine under what conditions a complete separation may be obtained for a given experimental system.
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  • 179
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    AIChE Journal 40 (1994), S. 1639-1649 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Elliptical basis function (EBF) networks are introduced as a new nonparametric method of estimating probability density functions for process data. Unlike Parzen window density estimators that use identical hyperspherical basis functions, the EBF method uses elliptical basis functions adapted to the local character of the data. This technique overcomes the spikiness problem associated with Parzen windows, where in high dimension, they can fail to produce smooth probability density estimates. The EBF estimator produces valid density functions that converage to the underlying distribution of the data in the limit of an infinite number of training examples. A technique based on statistical cross validation is introduced for evaluating different density estimators. The criterion is a measure of how well the density estimator estimates the density of data not used in the training. The EBF density estimation method and the evaluation technique are demonstrated using several examples of fault diagnosis.
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  • 180
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    AIChE Journal 40 (1994), S. 120-130 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Spatiotemporal patterns existing in a one-dimensional fixed-bed reactor with oscillatory or excitable kinetics are analyzed to develop the methodology of motion identification and classification. The reactor model accounts for a local (solid-phase) oscillator and a global (gas-phase) convective interaction. The local oscillator incorporates a fast and diffusing surface temperature and a localized activity as its dynamic variables. Such kinetics admit a traveling pulse solution or homogeneous oscillations in a uniform medium. In a fixed-bed reactor, the local conditions in the bed (the phase plane character) vary along the system. The response of an excitable bed to local perturbations depends on its location (at inlet or outlet) and the nature of the initial steady state ( ignite or extinguished). The main spatiotemporal-sustained patterns in the bed are: almost homogeneous oscillations that appear as parallel bands in the time-space contour map; oscillatory fronts that emerge from the reactor exit, and aperiodic motion that appears as split-bands. Pattern selection is determined by the phase planes spanned by the reactor and the ratio of the two slowest time scales: front residence time and period of oscillations.
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  • 181
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    AIChE Journal 40 (1994), S. 131-142 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Thermolysis of coal yields a complex mixture of many extract products whose molecular-weight distribution (MWD) varies with time for continuous-flow, semi-batch experiments. A laboratory flow reactor with a differential fixed bed of coal particles contacted by supercritical tert-butanol was used to provide dynamic MWD data by means of HPLC gel permeation chromatography of the extract. The experimental results, multipeaked, time-dependent MWDs of extract molecules, are interpreted by a novel mathematical model based on continuous-mixture kinetics for thermal cleavage of chemical bonds in the coal network. The parameters for the MWDs of extractable groups in the coal and the rate constants are determined from the experimental data. The effect of temperature on the kinetics of the extraction is explained in terms of one- and two-fragment reactions of the extractable groups in the coal. At lower temperatures (613 and 633 K) single-fragment reactions dominate, but at higher temperatures (653 and 673 K) more bonds in the coal are broken and the two-fragment reactions become significant. Also, the detailed MWDs are related to conventional lumped data for the thermolytic extraction process. The results yield information about the structure of coal, as well as the kinetics and mechanism of supercritical thermolytic reactions.
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  • 182
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    AIChE Journal 40 (1994), S. 143-151 
    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 flue gas desulfurization process being developed for coal-fired power plants removes and concentrates sulfur oxides (SOx). The key element is an electrochemical cell using a sulfur oxide selective membrane. It achieves 90% sulfur oxide removal with near 100% electric current efficiency.Recent research has focused on improving the structure of the electrochemical membrane and its interface with the electrodes. The capillary forces of the membrane and porous electrodes establish an equilibrium. To maintain electrode surface area enhancement, it is necessary to retain the electrolyte in the membrane and allow only wetting of the electrode pores. Chemically-stable matrix materials for the membrane have been identified; several fabrication techniques were used to prepare the actual membrane structure. A new electrode material, (LiO)xNiO, possesses the proper chemical stability and electrical properties in the corrosive environment. These modifications have led to an order of magnitude increase in flux and operating lifetime.
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    AIChE Journal 40 (1994), S. 178-181 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 184
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    AIChE Journal 40 (1994), S. 192-192 
    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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  • 185
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    AIChE Journal 40 (1994), S. 2055-2059 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 186
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    AIChE Journal 40 (1994), S. 2060-2064 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 187
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    AIChE Journal 40 (1994), S. 2045-2054 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In spite of the increasing commercial use of zeolites for binary and multicomponent ion exchange, understanding of the basic mass-transfer processes associated with multicomponent zeolite systems is quite limited. This study evaluates Na-Ca-Mg-Cs-Sr ion exchange from an aqueous solution using a chabazite zeolite. Mass-transfer coefficients are determined from experimental batch-reactor data for binary and multicomponent systems. The experimental data indicate that diffusion through the microporous zeolite crystals is the primary diffusional resistance. Macropore diffusion also significantly contributes to the mass-transfer resistance. Various mass-transfer models are compared with the experimental data to determine values for intraparticle diffusivities. Effective diffusivities obtained accurately predict experimental data using a variety of models. Only the model accounting for micropore and macropore diffusion occurring in series accurately predict multicomponent data using diffusivities from the binary system. Liquid and surface diffusion both contribute to macropore diffusion. Surface and micropore diffusivities are concentration-dependent for the system of interest.
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  • 188
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    AIChE Journal 40 (1994), S. 862-869 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A novel perfectly mixed laboratory reactor for determining kinetics of heterogeneously catalyzed gas-phase reactions has been developed. Perfect mixing is achieved by circulating the gas in the reactor using an axial flow impeller in a well streamlined enclosure. Pellets are fixed in a rectangular opening in the blades of the impeller. They rotate with the impeller, thus realizing high particle velocities in the reactor. Interparticle mass transfer was studied experimentally by vaporization of naphthalene pellets. The mass-transfer coefficient in the novel reactor was found to depend on the velocity of a particle in the reactor. Mass-transfer coefficients in an internal recycle reactor at equal impeller tip speeds are 4-6 times lower than those in the novel reactor, and conditions can be chosen easily where at higher rotational speeds the mass- and heat-transfer rates are 8-10 times higher than in classical recycle reactors. The recycle flow rate in a recycle reactor was found to depend strongly on the resistance to flow caused by the catalyst bed itself. The novel reactor was tested under reacting conditions using the hydrogenation of ethene.
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    AIChE Journal 40 (1994), S. 878-887 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In this work we present an extension of the statistical associating fluid theory (SAFT) developed for associating fluids by applying this extension to polymer solutions and blends. The polymer molecule is modeled as a flexible chain made of bonded spherical segments. These segments interact with the Lennard-Jones potential. The extension of SAFT is compared with molecular simulation results for polymer solutions and blends. Since the same force model is used in the simulation and theory, this comparison is a strong test of the assumptions made in deriving the theory. Results are presented for pure polymers of up to 50 segments long, polymer solutions of a polymer 20 segments long dissolved in its own monomer, and blends of polymers of 25 segments each. The theory produces results that are in better agreement with simulation results than the Flory-Huggins theory for the systems studied.
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    AIChE Journal 40 (1994), S. 521-535 
    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 oxidative coupling of methane was carried out in the absence of catalyst in a continuous flow setup at total pressures up to 1,000 kPa, temperatures from 950 to 1,230 K, and inlet molar ratios of CH4/O2 down to 2.5. At constant temperature and residence time, the conversions of methane and oxygen increase drastically with increasing pressure. At oxygen conversions higher than 80%, product selectivities are comparable at different pressures. The space-time yield of the C2 products reaches a level comparable to that required for industrial operations from 400 kPa on. A radical-reaction network consisting of 38 elementary reactions allows to describe the experimental data. To describe adequately the effect of total pressure, the pressure fall-off behavior of the rate coefficients for the unimolecular reactions in the network has to be taken into account explicitly.General features of the reaction mechanism do not depend on the total pressure. Methyl and hydrogen peroxy radicals are the most abundant radicals. The total pressure increase results in a drastic increase of the concentrations of the chain carriers, particularly the hydrogen peroxy radical. Higher pressure favor the oxidative route from ethane to ethylene compared to the pyrolytic route. Increasing the total pressure leads to an increase of the primary and a decrease of the consecutive CO formation relative to the coupling. The balance between these nonselective routes determines the effect of the total pressure on the integral selectivity to C2 products at different conversions. The major contribution to the integral CO selectivity comes from the oxidation of methyl radicals.
    Additional Material: 8 Ill.
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  • 191
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 543-555 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Phase behavior data and FTIR spectra along with solubilities and solvatochromic shifts of ionic indicator dyes are reported for binary, ternary and quaternary systems composed of pentaethylene glycol n-octyl ether (C8E5), CO2, water, and n-pentanol as a function of temperature, pressure and composition. With the addition of n-pentanol as a cosurfactant, the water to surfactant ratio, W0, reaches values as high as 12. As water is added further, a surfactant-rich phase precipitates due to micellemicelle interactions. Ionic dyes are soluble at levels of 0.03 mM, far in excess of the negligible solubility in pure CO2.
    Additional Material: 17 Ill.
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  • 192
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 193
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 577-585 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Diffusivities of oxygen, nitrogen and their mixtures in carbon molecular sieve are measured under conditions used for kinetic separation of air by adsorption (elevated pressures). In binary diffusion, codiffusion enhances fluxes for both components, whereas counterdiffusion has the opposite effects; for both cases, the effects are significantly more pronounced for the fast diffusing component. The multicomponent diffusion theory developed earlier in this laboratory for surface diffusion is reformulated for diffusion in molecular sieves. Multicomponent diffusivities can be predicted from the following pure-component information: concentration-dependent diffusivities and diffusional activation energies. Predicted binary diffusion results agree fairly with the experimental data for oxygen and nitrogen in carbon molecular sieve.
    Additional Material: 15 Ill.
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  • 194
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 957-965 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A study of flash equations associated with multicomponent systems that can form three phases at a given temperature and pressure indicated that different equations are needed at different boundaries of the solution space. This problem dictates that one- and two-phase trial solutions be obtained first on the boundaries prior to a search in the three-phase interior region. Two new formulations of the flash equations have been developed to avoid this problem. Solutions at boundaries as well as those in the three-phase region can now be obtained with a single search procedure. The new formulations are made using functions that are monotonic in the selected coordinates. These properties facilitate the use of nested, single-variable search methods. Interpolating with second-order functions, when applicable, nested search methods are often faster than two-dimensional simultaneous search methods. Tests of these formulations have demonstrated the advantages of these characteristics.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
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  • 195
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 613-620 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An advanced process is developed for the separation of H2S from natural gas through an electrochemical membrane. H2S is removed from natural gas by reduction to the sulfide ion and H2 at the cathode. The sulfide ion migrates to the anode through a molten salt electrolyte suspended in an inert ceramic matrix. Once at the anode it is oxidized to elemental sulfur and swept away for condensation in an inert gas stream. The natural gas is enriched with H2. Order-of-magnitude reductions in H2S concentration have been repeatedly recorded on a single pass through the cell. This process allows removal of H2S, while producing H2 and elemental sulfur directly. No absorbents are used, and there is no need for subsequent treatment of a concetrated H2S stream as with conventional gas sweetening technology. This makes the process economically attractive, since it is much less equipment-intensive than conventional technology.
    Additional Material: 9 Ill.
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  • 196
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 627-646 
    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 Åström-Hägglund autotuner is extended to multivariable systems. The proposed multivariable automatic tuning performs the identification-design procedure in a sequential manner. Its advantages are discussed, as well as the process characteristics resulted from sequential design. One important feature is that the sequential design often leads to underdamped process characteristics. Given these characteristics, potential problems in the Ziegler-Nichols tuning are discussed and a modification is made. The sequential identification and the modified Ziegler-Nichols controller design method form the basic structure for the multivariable autotuner. The properties of convergence, the implications of tuning sequence, and the indications of undesirable pairing for the autotuner are explored. Consequently, a multivariable autotuning procedure is proposed. Two nonlinear distillation examples and a 3 × 3 linear system are used to illustrate the effectiveness of the autotuner. Simulation results show that good performance can be obtained with minimal engineering effort and the autotuner works well for very difficult processes in a very simple way.
    Additional Material: 24 Ill.
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  • 197
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1118-1137 
    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-step (feed, delay, and purge), one-column pressure swing adsorption reactor has been analyzed. An equilibrium model taking into account species mass balances, overall mass balance, momentum balance, reaction rate, and nonlinear multicomponent adsorption equilibrium isotherms was derived to describe the PSA reactor process. Numerical solution of model equations was obtained by using the method of orthogonal collocation on finite elements, and simulation results showed that 10-20% higher conversion than reaction equilibrium conversion in a fixed-bed reactor could be obtained from the PSA reactor for a reversible reaction A ⇄ B + C, such as dehydrogenation of ethane to ethylene and hydrogen on cadmium-exchanged zeolites, where only product B was assumed to be adsorbed. When both reactant A and product B are adsorbed, 10% higher conversion over the reaction equilibrium limit was observed for pure reactant feed. The effects of system and operating parameters on the process performance of the PSA reactor have been studies, as well as the bed dynamics of the PSA reactor at the cyclic steady state.
    Additional Material: 20 Ill.
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  • 198
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1246-1253 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Devonian shales and other unconventional resources can be highly fractured and may have significant amounts of gas stored by adsorption. Conventional experiments are not well suited for characterizing the properties important for describing gas storage and transport in these media. Here, X-ray computed tomography scanning is used to determine gas storage in dynamic gas flow experiments on Devonian shale samples. Several important properties are obtained from these experiments, including fracture widths, adsorption isotherms, and matrix porosities and permeabilities.
    Additional Material: 8 Ill.
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  • 199
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1262-1267 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Magnetic resonance imaging is used to make nondestructive experimental measurements of fluid flow velocity and rock porosity inside a brine-filled Casper sand-stone sample during brine injection. Two-dimensional images of these values are obtained in arbitrary cross sections, with pixel sizes on the order of 1 mm2. The data are then statistically analyzed to find the variation of the average interstitial velocity as a function of porosity, as well as frequency distributions for both the velocity and porosity. The results show that as local porosity increases, the local flow velocity increases, according to the empirical relationship, V = 0.0669 φ + 0.0055. Thus, higher porosity regions of the core are better contacted by the displacement fluid. Results also imply bypassing of fluid around the perimeter of the core, indicating the need for a coreholder capable of sustaining higher overburden pressures on the order of 225 psi (1.55 MPa).
    Additional Material: 8 Ill.
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  • 200
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1254-1261 
    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 fourth-generation X-ray computer-assisted tomography (CAT) scanner was used for the study of fluidized and trickle beds. A variety of exploratory experiments were performed, and images of density and holdup were obtained in three dimensions as a function of time. The gas/solid fluidized beds were glass bead/nitrogen and polyethylene/nitrogen systems. The trickle bed was a glass bead/nitrogen/water system. The algorithms presented can be used to determine holdup from X-ray absorption data. These algorithms - extensions of similar algorithms used for the calculation of fluid saturations in porous media - are applied on data of CAT scanner images as they are generated by the scanner and after they are transferred to a workstation. The results of the presented tests demonstrate how detailed holdup calculations can be performed in a chemical reactor. Radial and longitudinal variances of the holdup can be easily defined. The proposed algorithms can assist in the design of chemical reactor prototypes.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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