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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Adsorption 6 (2000), S. 169-174 
    ISSN: 1572-8757
    Keywords: adsorption ; WS2 ; nanotubes and fullerenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Adsorption-desorption cycles were measured for methane on non-irradiated WS2, and on irradiated WS2 (which contained, in part, WS2 fullerenes and nanotubes). Both types of samples were further subdivided into three sets: one set received no further treatment, another set was heated under vacuum, and the last set was acid-treated and heated. The specific surface area was determined for each set; so was the presence or absence of a hysteresis loop in the adsorption-desorption cycles. The results of these two groups of measurements were correlated with the space available for adsorption. The implications of the results for the experimental determination of the dimensionality of gas adsorbed at the interior of nanotubes are discussed.
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  • 2
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    Adsorption 6 (2000), S. 137-147 
    ISSN: 1572-8757
    Keywords: adsorption ; kinetics ; linear driving force model ; process design
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Linear Driving Force (LDF) model for gas adsorption kinetics is frequently and successfully used for analysis of adsorption column dynamic data and for adsorptive process designs because it is simple, analytic, and physically consistent. Yet, there is a substantial difference in the characteristics of isothermal batch uptake curves on adsorbent particles by the LDF and the more rigorous Fickian Diffusion (FD) model. It is demonstrated by using simple model systems that the characteristics of the adsorption kinetics at the single pore or the adsorbent particle level are lost in (a) evaluating overall uptake on a heterogeneous porous solid, (b) calculating breakthrough curves from a packed adsorbent column, and (c) establishing the efficiency of separation by an adsorptive process due to repeated averaging of the base kinetic property. That is why the LDF model works in practice.
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  • 3
    ISSN: 1572-8757
    Keywords: silical glasses ; CPG ; Vycor ; adsorption ; capillary condensation ; molecular simulation ; Monte-Carlo ; SANS ; SAXS ; fractals ; surface roughness ; Porod's law ; Gurvitch rule ; hysteresis loop
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract We have performed atomistic Grand Canonical Monte-Carlo (GCMC) simulations of adsorption of xenon in a Vycor-like matrix at 195 K. The disordered mesoporous network is obtained by applying a numerical 3D off-lattice reconstruction procedure to a simulation box originally containing silicon and oxygen atoms of a non-porous silica solid. In order to reduce the computational cost, we have applied a homothetic decrease of the simulation box dimensions which preserves the morphology and the topology of the pore network (the average pore dimension is then around 30 Å). The surface chemistry is obtained in a realistic fashion by saturating all dangling bonds with hydrogen atoms. Small angle scattering spectra calculated on different numerical samples have evidenced a departure from Porod's law due to surface roughness. The simulated isotherms calculated on such disordered connected porous networks, show the capillary condensation phenomenon. The shape of the adsorption curves differs from that obtained for simple pore geometries. The analysis of the adsorbed quantity distribution indicates partial molecular-film formation depending on the local surface curvature and roughness.
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  • 4
    ISSN: 1572-8757
    Keywords: adsorption ; zeolite ; chlorodifluoromethane ; adsorption structure ; H and F NMR ; chemicalshift ; relaxation time ; adsorbate mobility
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The adsorption of CHClF2 on NaY5.6 zeolite has been studied by measuring the H and F NMR of the adsorbed CHClF2, focusing in particular on the measurements of the chemical shift and longitudinal relaxation time, as well as the adsorption isotherm measurements. It is possible to determine the coordination structure of the CHClF2 adsorbed on NaY5.6 zeolite by measuring the adsorption amount dependence of the chemical shift. In addition, the motional activity of the adsorbed molecules in the super cage of the zeolite is discussed on the basis of observed longitudinal relaxation times for various adsorption amounts.
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  • 5
    ISSN: 1572-8757
    Keywords: adsorption ; EPR ; mordenite ; MOR ; NO ; zeolite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Adsorption isotherms of nitrogen monoxide (NO) and in situ EPR spectra of adsorbed NO on mordenite zeolites (MOR) of different cation types (HM, NaM and CaM) are measured at different temperatures to elucidate the effect of the strong adsorption promoted by the enhancement of potential field in micropore of MOR (micropore filling) as well as the electrostatic interaction in MOR on NO adsorption. The NO molecules adsorb irreversibly and fill up the micropore of MOR at 201 K, above the critical temperature of NO, regardless of the kind of cation species. The NO adsorption takes place even at 273 K. In the adsorption at 273 K, the strength of electrostatic field formed by cation sites affects the adsorptivity and the order of saturation amount of adsorption (V s) corresponds to that of the electrostatic field strength. EPR results show that NO molecules strongly interact with cation sites in MOR and disproponation reaction of NO take place on CaM.
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  • 6
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    Adsorption 6 (2000), S. 159-167 
    ISSN: 1572-8757
    Keywords: silicalite-1 ; adsorption ; TEOM ; alkanes ; isosteric heat ; adsorption entropy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The equilibrium adsorption of the light alkanes methane, ethane, propane, n-butane, and i-butane in silicalite-1 has been investigated using the TEOM technique. Either a conventional or a dual-site Langmuir isotherm appropriately describes the equilibrium data. Good agreement with the literature data determined by other techniques indicates the TEOM is a reliable technique. The adsorption of i-butane in silicalite-1 reveals the discrete preferential molecular siting, implying a discrete-dual-structural heterogeneity for light alkanes in silicalite-1.
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  • 7
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    Adsorption 6 (2000), S. 325-335 
    ISSN: 1572-8757
    Keywords: copper ; ca-koalinite ; adsorption ; desorption ; thermodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The temperature effect on Cu adsorption and desorption on kaolinite has been investigated at four temperatures (8°C, 25°C, 30°C and 40°C). The clay sample was saturated with Ca. Copper was sorbed from solutions containing eleven Cu concentrations between 0.0010 and 0.0211 M, equilibrated for 2 days. Cu adsorption decreased, but desorption increased with increasing temperature, indicating that adsorption is an exothermic process while desorption is endothermic. These conclusions are confirmed by the values of ΔH 0 estimated for adsorption and desorption. The initial copper concentration is a significant factor influencing mainly the adsorption process, which is spontaneous (ΔG 0 〈 0) only for low initial Cu concentrations. The desorption process is spontaneous for all Cu concentrations. ΔS 0 values have also been calculated. Experimental adsorption data were successfully fitted to the Freundlich isotherm and to the Gouy-Chapman model in order to express the process quantitatively.
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  • 8
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    Adsorption 6 (2000), S. 349-357 
    ISSN: 1572-8757
    Keywords: sulfadiazene ; adsorption ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract To investigate the nature of interactive forces between sulfadiazene molecules and alumina surface the experiments were performed for the adsorption of sulfadiazene (SD) from its aqueous sulution onto the alumina surfaces at 25 ± 0.2°C and the influence of factors such as increasing concentration of SD (4.0–20.0 × 10−3 mol cm−3), the time required for adsorption equilibrium, pH (2.0–12.0) and temperature (5–45°C) of the adsorption medium, the presence of ions like Cl−, SO2− 4 and PO3− 4 (0.01–0.30 M) and organic solvents (5% v/v) were observed on the course of adsorption of SD. Various adsorption and kinetic parameters such as adsorption coefficient, the rate constants for adsorption and desorption were also evaluated. The results of the above cited studies facilitated to formulate the mechanisms of interaction between SD and alumina surfaces. From application view point the present work may be a potential tool for an effective chromatographic separation of sulfa drugs from industrial effluents.
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  • 9
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    Adsorption 5 (1999), S. 183-192 
    ISSN: 1572-8757
    Keywords: adsorption ; activated carbon ; neural network ; ideal adsorption solution theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Three neural network models were used for prediction of adsorption equilibria of binary vapour mixtures on an activated carbon. The predictions were compared both with published experimental data and calculated values from the Ideal Adsorption Solution (IAS) model. The neural network was trained using both binary and single component experimental adsorption data. Even for a limited number of data points (about 60) the network models were capable of approximating experimental data very precisely.
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  • 10
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    Adsorption 5 (1999), S. 261-278 
    ISSN: 1572-8757
    Keywords: adsorption ; concentrated systems ; pressure transients ; flow transients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A study of the occurrence of large pressure and flow transients when a strongly adsorbed gas is fed to a column which is initially loaded with a lightly adsorbed gas is presented here. Under certain conditions, these transients can cause premature breakthrough and change the shape of the breakthrough curve. This will result in improper estimation of adsorption parameters by the dynamic column loading method and lower apparent adsorption capacity in a full scale unit. A data acquisition system was used to record the pressure and flow transients. An isothermal PDE model developed to study these transients agreed reasonably well with the nonisothermal experimental results. The PDE model predicts that pressure and flow transients will occur during step and pulse~tests conducted to obtain adsorption and mass transfer parameters by the chromatographic method. For instance, lower adsorption capacity will be realized during step tests due to lowering in column pressure. Oscillations were observed when columns are connected in series. The PDE model also predicts these oscillations. Simulations indicate that the extent of oscillations is dependent on the dead volume between columns.
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  • 11
    ISSN: 1572-8757
    Keywords: micropore size distribution ; activated carbon ; adsorption ; desorption ; equilibrium ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract This paper deals with the prediction of adsorption equilibrium and kinetics of hydrocarbons onto activated carbon samples having different micropore size distribution (MPSD). The microporous structure of activated carbon is characterised by the distribution of slit-shaped micropores, which is assumed to be the sole source of surface heterogeneity. The interaction between adsorbate molecule and pore walls is described by the Lennard-Jones potential theory. Different adsorbates have access to different pore size range of activated carbon due to the size exclusion, a phenomenon could have a significant influence on both multicomponent equilibria and kinetics. Activated carbons with three different MPSDs are studied with ethane and propane as the two model adsorbates. The Heterogeneous Macropore Surface Diffusion model (HMSD) is employed to simulate adsorption kinetics. The simulation results show that the MPSD is an important factor affecting both the multicomponent equilibria and kinetics.
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  • 12
    ISSN: 1572-8757
    Keywords: adsorption ; molecular simulation ; activated carbon ; surface oxygen ; alkaloids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The influence of the density and the type of surface oxygen on the adsorption of berberine alkaloid onto activated carbon was investigated using the molecular dynamics simulation method in vacuum. The carbon surface consisted of a basal plane of graphite and surface oxygen groups which were bonded on the graphite plane in a regular square array with various densities. Two types of surface oxygen groups, =O and —OH, were employed. The simulation results showed that the berberine alkaloids were favorable to be adsorbed on the negative charged carbon surfaces. It was indicated that the vdw attraction of the carbon surface to the alkaloid molecule dominates the adsorption only at the lower surface density of oxygen. It is also indicated that a good adsorptive selectivity for a certain berberine alkaloid can be obtained by controlling the density of surface oxygen. The adsorption simulation of berberine alkaloids onto activated carbon in the presence of water was also carried out by using a dome-shape molecular model for presenting the alkaloid/water/carbon system. It was found that the adsorption of berberine alkaloids on the activated carbon which has a higher density of surface oxygen was strongly inhibited by the presence of water.
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  • 13
    ISSN: 1572-8757
    Keywords: kinetics ; isotope-exchange ; nitrogen ; adsorption ; methane ; zeolite ; equilibria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Isotope Exchange Technique (IET) was used to simultaneously measure pure and binary gas adsorption equilibria and kinetics (self-diffusivities) of CH4 and N2 on pelletized 4A zeolite. The experiment was carried out isothermally without disturbing the adsorbed phase. CH4 was selectively adsorbed over N2 by the zeolite because of its higher polarizability. The multi-site Langmuir model described the pure gas and binary adsorption equilibria fairly well at three different temperatures. The selectivity of adsorption of CH4 over N2 increased with increasing pressure at constant gas phase composition and temperature. This curious behavior was caused by the differences in the sizes of the adsorbates. The diffusion of CH4 and N2 into the zeolite was an activated process and the Fickian diffusion model described the uptake of both pure gases and their mixtures. The self-diffusivity of N2 was an order of magnitude larger than that for CH4. The pure gas self-diffusivities for both components were constants over a large range of surface coverages (0 〈 θ 〈 0.5). The self-diffusivities of CH4 and N2 from their binary mixtures were not affected by the presence of each other, compared to their pure gas self-diffusivities at identical surface coverages.
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  • 14
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    Adsorption 5 (1999), S. 159-167 
    ISSN: 1572-8757
    Keywords: impedance spectroscopy ; uptake curve ; adsorption ; polarization of adsorbate ; dielectric properties of adsorbed phases
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Physisorption equilibria of gases on inert porous solids like activated carbon or molecular sieves can be characterized by measuring the (frequency dependent) capacitance of a capacitor filled with a sample adsorbent. This quantity strongly depends not only on the physico-chemical structure of the empty adsorbent in vacuum, but also on the permanent or induced dipole moments of the molecules adsorbed and of the fluid phase. Consequently, it should be possible to determine the excess mass being adsorbed on the internal surface of a highly porous solid by measurements of the dielectric constant. The aim of this work is to show for various pure gases and adsorbents that the change of the capacitance of an adsorption system depends on the adsorbed mass. Therefore, this effect can be used to characterize porous solids and their adsorbates and, for example, to check the state or the quality of industrial adsorbents during a process on site if calibration measurements have been taken (Staudt et al., 1994, 1998).
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  • 15
    ISSN: 1572-8757
    Keywords: zeolites ; polar compounds ; adsorption ; adsorption isotherms ; equilibrium ; liquid phase ; breakthrough curves ; acetonitrile ; acrylonitrile ; dioxane ; ZSM-5 ; MCM-22 ; Na-X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The liquid phase removal of low concentrations of polar compounds (acetonitrile, acrylonitrile and dioxane) from toluene by adsorption on zeolites reveals very high selectivity factors. Kinetic selectivity factors as high as 16,100 are observed. The selection of the zeolites (MFI, MWW and FAU type) allowed the study of the effects of varying aluminum content, the presence and absence of acidic centers and varying pore volumes. To assess the relative effectiveness of each adsorbent, both equilibrium and continuous flow, pseudo equilibrium, breakthrough experiments were conducted. The continuous flow experiments were carried out at 25 and 75°C. The zeolites H-ZSM-5, H-MCM-22 and Na-X are highly effective in removing the polar compounds from toluene to a concentration level down to less than 20 ppm (detection limit). The results obtained with the equilibrium batch experiments are confirmed by the continuous flow breakthrough experiments.
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  • 16
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    Adsorption 4 (1998), S. 25-33 
    ISSN: 1572-8757
    Keywords: hydrophobic zeolites ; breakthrough curves ; adsorption ; binary mixtures ; modeling ; overall mass transfer ; roll-up
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Breakthrough curve measurements of SO2 and water vapor were carried out on a number of selected mordenite and pentasil zeolites from their binary and ternary mixtures with CO2 at 50 and 100°C. SO2 capacities of these samples were found to be significantly reduced by the presence of water. Competitive adsorption led to unusually high overshoot peaks of SO2 breakthrough curves. On the other hand, SO2 was found to displace water on the samples with very high silica to alumina ratio. A linear driving force, isothermal model was used to predict the breakthrough curves. Langmuir and extended Langmuir equilibrium models were used to describe the equilibrium properties of water and SO2, respectively. The overall mass transfer resistance obtained from the model was compared to the values calculated from a simplified biporous adsorbent model to shed some light on the adsorption kinetics.
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  • 17
    ISSN: 1572-8757
    Keywords: wool ; water vapour ; adsorption ; diffusion ; column dynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Adsorption of water vapour on wool provides not only textile comfort, but also convenience in transportation due to increase in its bulk density. The adsorption and desorption isotherms of water vapour for wool were determined by both volumetric technique using a Coulter Omnisorp 100CX instrument and gravimetric method employing a Cahn 2000 electronic microbalance. Adsorption isotherm fitting to B.E.T. model and hysteresis on desorption was observed. The average effective diffusion coefficient of water in wool was found to be 8.4 × 10-14 m2s-1 at 25°C from gravimetric data. The effects of packing height and air velocity on the breakthrough curves were also investigated in the wool packed columns. For pseudo first order model, k values changing between 0.33 × 10-6 − 69 × 10-6 s-1 was obtained for 2.2–6.4 cm s-1 air velocity and 0.05–0.20 m packing height ranges.
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  • 18
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    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 59 (1998), S. 451-460 
    ISSN: 0006-3592
    Keywords: protein fouling ; membrane transport ; ultrafiltration ; adsorption ; filtration ; composite membrane ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Protein fouling can significantly alter both the flux and retention characteristics of ultrafiltration membranes. There has, however, been considerable controversy over the nature of this fouling layer. In this study, hydraulic permeability and dextran sieving data were obtained both before and after albumin adsorption and/or filtration using polyethersulfone ultrafiltration membranes. The dextran molecular weight distributions were analyzed by gel permeation chromatography to evaluate the sieving characteristics over a broad range of solute size. Protein fouling caused a significant reduction in the dextran sieving coefficients, with very different effects seen for the diffusive and convective contributions to dextran transport. The changes in dextran sieving coefficients and diffusive permeabilities were analyzed using a two-layer membrane model in which a distinct protein layer is assumed to form on the upstream surface of the membrane. The data suggest that the protein layer formed during filtration was more tightly packed than that formed by simple static adsorption. Hydrodynamic calculations indicated that the pore size of the protein layer remained relatively constant throughout the adsorption or filtration, but the thickness of this layer increased with increasing exposure time. These results provide important insights into the nature of protein fouling during ultrafiltration and its effects on membrane transport. © 1998 John Wiley & Sons, Inc. Biotechnol Bioeng 59:451-460, 1998.
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  • 19
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    Biotechnology and Bioengineering 60 (1998), S. 434-444 
    ISSN: 0006-3592
    Keywords: immobilized enzymes ; organic solvents ; esterification ; water ; adsorption ; adsorption modeling ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Reducing the influence of an undesired product in an enzymatic reaction could have a significant impact on the productivity of such systems. Here, we focus on the removal of water formed during an enzymatic esterification in a batch reactor. A commercial immobilized lipase preparation, known as Lipozyme, is used as the biocatalyst and propionic acid and isoamyl alcohol dissolved in hexane are the substrates. In this system, the water formed will partition between the catalyst and the medium. As the more polar reactants are converted into the less polar ester product, the water is partitioned more towards the biocatalyst and the accumulation of water eventually causes lower reaction rates. Addition of a strong-acid cation exchange resin in sodium form is found to control the water accumulation on the biocatalyst without stripping the essential water needed for the enzyme to function and substantial improvements in conversion are achieved. A mathematical model is developed to describe the batch reaction behavior with and without added absorbent, which successfully predicts the behavior of water and its effects. © 1998 John Wiley & Sons, Inc. Biotechnol Bioeng 60: 434-444, 1998.
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  • 20
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    Process Safety Progress 17 (1998), S. 61-67 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Risk assessments have been performed to determine the risk associated with the transportation of hazardous wastes through a city. In the course of these assessments, a number of modeling issues arose relating to transportation accident rates, the characterization of incidents, the effect of thermal radiation, the impact of exposure to toxic chemicals, and the threshold for acceptable risk. This paper discusses these issues.
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  • 21
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    Process Safety Progress 17 (1998), S. S3 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 22
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    Process Safety Progress 17 (1998), S. 98-103 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper presents the design of ribbon wound pressure vessels useful for Ammonia, Urea and Methanol plants. The design is to create a thin shell of 1/5 the total wall thickness required, weld it to the end pieces, and wind 4 to 8 mm thick ribbons of 80 mm width at an angle of 15 to 30 degrees on the inner shell, using a prestress. The ribbons are welded at the ends and an even number of layers are wound cross-helically on to the shell. With more than 7000 vessels over the pressure range of 50 to 350 atmospheres in use in the various chemical industries in China over the past 30 years, their safety record has been excellent. Of particular interest has been the application of this technology in the Ammonia and Urea plants, where the design allows fabrication of these vessels at substantial reduction in cost, and early delivery, when compared to the mono wall technology.
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  • 23
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    Process Safety Progress 17 (1998), S. 20-22 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Most audits try to look at a representative selection of the plant procedures and equipment. An alternative is a survey, a look in depth at selected procedures (such as those for testing alarms and trips, issuing permits-to-work, controlling modifications, taking samples or testing relief devices) or selected equipment (such as level glasses or equipment for handling LPG). If the procedure or equipment is well-chosen, surveys may make a bigger contribution to safety, per person-hour, than a conventional audit.
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  • 24
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    Process Safety Progress 17 (1998), S. 39-42 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Under OSHA 1910.119, all Process Safety Management (PSM) facilities are required to keep their pressure relief system design information current. This article demonstrates why a pressure relief system design verification effort must be based on an equipment list, rather than a relief device list, in order to ensure that every piece of equipment is adequately protected. The formerly common practice of simply checking the design bases of all existing relief devices is deficient is deficient since this technique does not systematically ensure that every piece of equipment is protected.The “Berwanger Method” is a step by step process for designing or analyzing a pressure relief system to meet OSHA 1910.119 Process Safety Information (PSI) and Process Hazard Analysis (PHA) mandates. The method uses a relational database which tracks the relationships between protected equipment, potential overpressure scenarios, and protective devices.The challenge facing an operating company does not end once the design basis has been “verified” - the design basis information must also be maintained and be readily accessible to avoid costly reinvention of the wheel down the road. The “Berwanger Method” also addresses these maintenance issues.
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  • 25
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    Process Safety Progress 17 (1998), S. 49-60 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper reports on a comprehensive literature search and small scale experimental work on the reaction characteristics of phosphorous trichloride and water. More than 30 tests were conducted, including both closed and open test cells. The water to phosphorus trichloride molar ratio was varied from 1 to 25. When in contact, water and phosphorus trichloride will form two liquid layers with a reaction starting at the interface. The impact of variables on reaction rates including the interface surface area, layer depth, and stirring were investigated experimentally. A reaction rate model that fits all the measured data is presented. Case studies illustrating the use of this data for emergency relief systems and vent containment design are presented in reference. [1].
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  • 26
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    Process Safety Progress 17 (1998), S. 68-73 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two major accidents in the 80's: the summit Tunnel Fire, England and Piper Alpha disaster, an offshore platform in the North Sea; and very recently, possible explosion of the Boeing, TWA flight 800 at New York, makes it imperative that further research into the mechonisms of the ignition of flammable vapor/air mixture in contact with hot surfaces needs to be done. There have been a number of studies of ignition by hot surfaces, but in all these studies the ignition sources were wire, sphere or strip, i.e., most of them were flat surfaces. But to the authors' knowledge, other variables which affect the ignition mechanism such as irregular geometrical shapes have not been studied. The purpose of this paper is to examine how the degree of confinement (or, configuration), size and orientation, of the heated surface affects the ignition temperature of the flammable vapors. The results were obtained by experimentnal and by computational fluid dynamics.
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    ISSN: 0006-3592
    Keywords: cellulose ; gel ; fiber ; immobilization ; adsorption ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: We prepared a new composite gel fiber by the gel formation of cellulose acetate and titanium iso-propoxide. The fiber is harder than alginate gel; it is also stable in common solvents, phosphate solution, and electrolyte solutions over a wide range of pH from 3 to 10. The fiber shows amphoretic adsorption properties depending on pH, namely, it acts anionic with decreasing pH and cationic with increasing pH. However, the fiber had no adsorption property for a pyrogen endotoxin. The β-galactosidase and α-chymotrypsin not retained in alginate gel were immobilized on the fibers by this method. The pH, temperature, and repeated run stabilities of the immobilized enzyme were compared to those of the native one. © 1998 John Wiley & Sons, Inc. Biotechnol Bioeng 59:651-656, 1998.
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    Process Safety Progress 17 (1998), S. S3 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    Process Safety Progress 17 (1998), S. 9-15 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The design and deflagration pressure relief vents is based on correlations developed for various types of combustible materials and for enclosures of different strengths. The primary guideline for deflagration vent design in the US is NFPA 68 Guide for Venting of Deflagrations [5]. That document gives guidance for the design of vents for enclosures containing flammable gases, specifically hydrogen, coke oven gas, propane, and methane. Application of the guide to other gases is achieved using the KG value. Values of KG are published for a relatively small number of gases, as seen in Table D-1 of NFPA 68. This work present KG data on several additional gases obtained in a laboratory scale test vessel along with analysis of the results with respect to published values of fundamental burning velocity.
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    Process Safety Progress 17 (1998), S. 23-31 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In May 1996, the Flammable and Combustible Liquids Code Committee of the National Fire Protection Association (NFPA) proposed for adoption by the Association a new edition of NFPA 30, Flammable and Combustible Liquids Code. This new edition was the culmination of two and one-half years' work by the Committee and included one of the most significant changes to that document in some twenty years: the incorporation of mandatory fire protection criteria for warehouses and other inside areas that store flammable and combustible liquids in containers and portable tanks.
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    Process Safety Progress 17 (1998), S. 32-38 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper describes the development of a risk ranked Inspection Recommendation procedure that is used by one of Exxon's chemical plants to prioritize repairs that have been identified during equipment inspection.As part of the Company's Safety Management Practices initiative in the late 1980's a procedure was put into place to ensure that an Inspector's repair recommendations were properly addressed by the organization. The initial procedures were successful at “systematizing” the documentation and stewardship-to-completion of the Inspector's recommendation, however, there were complications with the original process: (1)The Inspector made a simple High, Medium or Low assessment of the priority/criticality of the recommendation. Frequently, this resulted in disagreements with Operations about the true priority of the recommendation.(2)If there was agreement on the priority of the recommendation, there was still disagreement on the relative rank within the priority-which high priority was the highest priority?(3)With limited funds to spend on repairs, it was (and is) important to make sure that the money was being spent on the highest risk items that had the greatest risk reduction/cost benefit ratio.To address these concerns, the procedure was modified to incorporate a risk assessment of the recommendation by both the Inspector and Operations. In the new procedure, the Inspector describes the deficiency that he/she finds and assesses the probability of failure within a certain time-frame. Operations must assess the consequences, from an environmental, safety and economics standpoint, were the failure to occur. These assessments are combined in the typical risk equation (risk = probability × consequences) to arrive at a severity index which serves to rank the recommendation relative to the other recommendations. Because Operations participates in the assessment there is very little disagreement about the priority of the recommendation. The severity index puts the recommendations in order so it is quite clear which are the highest priority recommendations. This process has helped to focus the entire organization on those deficiencies that represent the greatest risk with the result that less time and money is spent correcting items that have a low risk/cost benefit ratio, allowing these savings to be used to reduce the higher risks in the plant.
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    Process Safety Progress 17 (1998), S. 124-126 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A simple analytical method is presented for estimating the hybrid minimum ignition energy (HMIE) of dust-gas mixtures, based on the assumed generality of Bartknecht's well-known test data for mixtures of propane with a series of dusts in air. Since the HMIE equation requires input data which might be unavailable, the use of conservative default methods is discussed.
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    Process Safety Progress 17 (1998), S. 138-148 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A large and potentially hazardous decrease in aldehyde autoignition temperature (AIT) occurs with increased pressure. The AIT-pressure curve determined in a 5 L stainless steel sphere was similar for propionaldehyde and butyraldehyde in air, falling from about 185°C at atmospheric pressure to 90°C at 140 psia. Reduction of oxygen concentration had little effect on propionaldehyde AIT. At 100°C and 140 psia, autoignitions accompanied by at least a doubling of pressure were observed above 4% oxygen. In the presence of a few grams of free liquid, propionaldehyde vapor ignited in air at initial conditions significantly below the AIT. The mechanism appears to involve rapid Fe-catalyzed exothermic liquid-phase oxidation leading to autoignition of the adjacent heated gas layer. An acetaldehyde vapor-air mixture in the presence of free liquid and rust exploded at room temperature when air pressure was increased to 95 psia; this result is discussed with reference to a cylinder overpressurization that occurred while making up an ostensibly sub-LFL calibration mixture with compressed air. Propionaldehyde's limiting oxygen concentration (LOC) was investigated in the near-autoignition region using the same 5L apparatus; the findings are discussed with reference to an overpressurization incident in an air-liquid partial oxidation reactor. The general results are used to illustrate the application of LOC in partial oxidation processes subject to autoignition and to discuss elements of the current ASTM draft test method for LOC, which does not address test difficulties associated with condensable and/or reactive gas systems.
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    Process Safety Progress 17 (1998), S. F3 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
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    Process Safety Progress 17 (1998), S. 157-170 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Risk analysis in chemical process industries is an elaborate exercise involving several steps from preliminary hazard identification to development of credible accident scenarios, to preparation of strategies for prevention or control of damage.All this requires substantial inputs of time and money. In order to get an approximate yet workable assessment of risk at much lesser costs, indices have been developed which link typical findings of elaborate risk analysis to scales of risk. The scales, in turn, provide workable measures of hazards/risks/safety.In the past, indices have been reported for swift risk assessment - the noteworthy among them include Dow fire and explosion index, Mond fire, explosion and toxicity index, IFAL index, and mortality index. A few rapid ranking techniques have also been proposed.This paper presents a new system of methodologies for Hazard Identification and Ranking (HIRA). The system consists of two indices: one for fire and explosion hazards and another for the hazard due to likely release of toxic chemical. The magnitudes of these indices indicate the severity of the likely accident; in terms of the size of the impacted area.HIRA has been applied to a typical chemical process industry - a sulfolane plant - and its performance has been compared with that of the Dow's and the Mond's indices. The study reveals that HIRA is more sensitive and accurate than the other indices.
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    Process Safety Progress 17 (1998), S. 200-208 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    Process Safety Progress 17 (1998), S. 213-218 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: On October 31, 1987 a crane lifting a heat exchanger convection section failed and severed a 4″ loading line and a 2″ pressure relief line to an HF alkylation reactor settler drum at a petroleum refinery in Texas City, Texas. Vapors were emitted under pressure for about two hours and the vessel was plugged and drained aproximately 44 hours later. A plume from this accidental release passed through residential areas, damaging some vegetation (brown lawns), and spawning a class action law suit. An extensive analysis was conducted to determine the total inventory loss and to model the blowdown process and the concentrations of HF in the plume. Since the discharge rate was decreasing with time, a peak concentration of HF in the emitted vapors occurred just before the water spray mitigation system became fully operative. Consequently, the mitigation efforts were more effective late in the response when concentrations were already low. The predicted plume concentrations are consistent with observed vegetation damage effects, with concentrations below Emergency Response Planning Guideline Level 3 past 3/4 mile from the source. These results support a policy of sheltering in place during such an event.
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    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A fifty-five gallon steel drum of a liquid organic peroxide pressurized and ruptured in the mix room of a manufacturing plant. The head of the drum blew off and the ejected material ignited. The resulting fire was extinguished by the building sprinkler system and operating personnel. Although there were no injuries, the fire caused significant damage in the mix room. The investigation of this incident, its likely cause, and the corrective actions will be discussed.
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    Process Safety Progress 17 (1998), S. 238-242 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Brazoria County Petrochemical Council, 13 companies that are working together to enhance relations between industry and the community, united in a joint effort at complying with the EPA's Risk Management Program. One of the significant issues the group had to address was the need to develop meaningful hazard assessment for presentation to the public. The EPA's “Table Look-Up Approach” found in the Offsite Consequence Analysis Guidance document is certainly a good tool; however, the built-in conservatism results in over-estimates of potential hazard areas. Much more meaningful results are shown to be obtained using one of the hazard release models.The value of using a credible scenario with realistic meteorological data is demonstrated through the consistently smaller areas predicted by the PHAST Model for planning purposes. Realistic scenarios/failure modes and realistic model parameters are important so that the risk to the public is not overstated. Proprietary models such as PHAST are invaluable in providing more meaningful consequences for planning purposes.
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    Process Safety Progress 17 (1998), S. 263-271 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Some of the hazards encountered by process plant operators involve the operation of in-line valves to control, start, and to stop flow. Torque required to operate valves may vary according to valve wheel size, in-line pressure, and valve flange position (open/closed). This study determined how valve wheel size, in-line pressure and valve position (open/closed) affect torque required to actuate a valve. Data were gathered with each combination of size, pressure and position for 336 valves in an operating petrochemical process facility. The results indicate that the main effects of valve wheel size, the in-line pressure, and open/closed valve position significantly affect operational torque requirements. In addition, the interaction between position and pressure was significant for operational torque. The implication of these results is that operators are exposed to operational torque requirements that exceed maximum acceptable capabilities that have been determined in previous studies.
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    Process Safety Progress 17 (1998), S. 288-296 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An ammonia storage tank was built at the BASF Antwerp site in 1969 on land reclaimed from the sea. After several years of operation uneven foundation settlement, of up 2, occurred. In order to assure stability of this area for the next operation period (at least 10 years) measures were taken to ensure continued safe operation. One key measure was strain gauge monitoring at the location of maximum stress.
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    Process Safety Progress 17 (1998), S. 297-301 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Baker-Strehlow methodology was developed to provide an objective approach to prediction of blast pressures from vapor cloud explosions. The complete methodology was first published in 1994 [1]. Since then, it has evolved through ongoing research and use in VCE hazard analyses, facility siting studies and accident investigations. This article gives a brief overview of a paper on recent developments in the Baker-Strehlow methodology presented at the 31st Loss Prevention Symposium in Houston on March 9-13, 1997. Because the entire paper is too lengthy to be presented here, the following discussions may be lacking in some details. A copy of the complete paper can be obtained from the American Institute of Chemical Engineers (AIChE).Since the Baker-Strehlow method was first published, it has been used extensively in VCE hazard assessments in refineries and chemical plants. As expected, many practical lessons have been learned during the course of the hazard assessments, and the Baker-Strehlow method has evolved as a result. The changes have been evolutionary, not revolutionary. In keeping with the goals of the original study in which the methodology was developed, all changes have been incorporated with the intent of achieving an objective methodology to provide consistent prediction of VCE blast effects.The revisions to the Baker-Strehlow method resulting from experience gained during plant walk-downs and hazard assessments include: Systematic identification of “potential explosion sites” or “PESs,”Selection of the level of confinement for mixed zones of 2D and 3D confinement,Deciding on flame expansion when confinement is elevated above the vapor cloud,Selecting the reactivity for a fuel that is a mixture of fuels with differing reactivities,Predicting blast loads when there are multiple PES's within a vapor cloud considering different ignition source locations.
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    Process Safety Progress 17 (1998), S. 83-85 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Safety, health and loss prevention are major areas of interst for the American Institute of Chemical Engineers (AIChE). There has been an evolution of these concerns over the years in the Institute just as it has in industry. This article chronicles this evolution.
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    Process Safety Progress 17 (1998) 
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    Keywords: Chemistry ; Chemical Engineering
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    Process Safety Progress 17 (1998), S. 1-8 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Recent guidelines released by the U.S. EPA define a worst-case scenario as a release under stable atmospheric conditions defined as Pasquil-Gifford stability class F. Unfortunately, very few tests at F stability have been available heretofore to provide a basis for models. Recent test data with propane releases by the German research organization TUV provide a set of 60 experiments conducted specifically to define the effects of atmospheric stability class on dispersion. Of these, 25 tests were at F stability. A comparable number were at each other stability class A through E. In addition 23 tests were at wind speeds under 1.5 m/s in stable atmospheres. This paper reports on adjustments made to our models based on these new data by reducing the originally-postulated sensitivity to stability class. In spite of considerable scatter in the TUV data, particularly between two different types of propane analyzers, the model allows us to extract information by averaging over the tests.
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    Process Safety Progress 17 (1998), S. 16-19 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A multi-disciplinary team developed a guideline for determining access restriction zones around vented solids handling equipment. The guideline provides a method for ensuring the discharge from a vented explosion will not cause injury to personnel. The steps in this method include: calculating the extent of external hazards from vented explosions; identifying potential areas where personnel could be exposed to a hazard; identifying ways to eliminate or reduce the hazard area; and establishing and documenting any access restrictions needed. Hazard zone calculations use the latest knowledge from research into fireball size, flame length and external pressure equations in VDI 3673. The guideline provides guidance for using this information. Options for mitigating or reducing external hazards from vented explosions are also described. As part of the project, the team audited several solids handling systems to look for potential oversights in existing restricted access areas. Some of the team's learnings from these audits are reviewed.
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    Process Safety Progress 17 (1998), S. 43-48 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper defines situation awareness (SA) and discusses its importance to operator-machine system safety and functioning in the context of process control activities. Specifically, identified are relationships of human detection of critical process cues converying the status of automated control systems and operator interpretation of the meaning and relevance of such information to the potential for negative incidents in chemical processing. Beyond individual operator SA in interacting with control systems, intra- and inter- work team SA are discussed for supporting individual attainment of process control responsibilities. Factors critical to team SA are discussed. “Road blocks” to team SA are also analytically examined. Lastly, methods for assessing individual and team SA are reviewed and vehicles for relating outcomes of these methods to changes in process control operator and team behavior to improve human-machine system safety and performance are relayed.
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    Process Safety Progress 17 (1998) 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    Process Safety Progress 17 (1998), S. 74-81 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The knowledge of the ingition behavior of dust-air mixtures due to electrical sparks (MIE, Minimum Ignition Energy) and hot surfaces (MIT, Minimum Ignition Temperature) is important for risk assessments in chemical production plants. The ignition behavior determines the extent and hence the cost of preventive protection measures.This paper describes the use of the minimum ignition energy and minimum ignition temperature as very important safety indexes in practice.Based on the latest results from large scale experiments on pneumatic filling of silos with polymeric materials and new results of full scale filling tests using Flexible Intermediate Bulk Containers (FIBC) manufactured from a variety of materials, guidance can be given to ensure safe operation in different situations such as filling, emptying operations, type of powder handled.The aim of this paper is to assist people dealing with product. It reflects the present state of the art and current knowledge of the assessment and measures associated with powder handling.
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    Process Safety Progress 17 (1998), S. 104-106 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In mid-1997, an Advanced Process Control (APC) scheme was implemented at a resins manufacturing complex with the goal of minimizing flare fuel gas usage while maintaining sufficient energy (BTU/SCF flare gas) to be in environmental regulatory compliance. Prior to APC implementation, the flare system was manually controlled by plant operators with minor attention paid to the minimization of fuel gas usage. Since implementation, APC has saved the plant thousands of dollars in fuel gas costs and reduced unnecessary combusted fuel gas emissions.Hazard analysis techniques were used in the development of the control scheme. An overview of the APC used, the economic evaluation, and the hazard analysis techniques used in the project are presented here.
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    Process Safety Progress 17 (1998), S. 107-123 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the risk assessment parlance, especially with reference to chemical process industries, the term “domino effect” is used to denote “chain of accidents,” or situations when a fire/explosion/missile/toxic load generated by an accident in one unit in an industry causes secondary and higher order accidents in other units. The multi-accident catastrophe which occurred in a refinery at Vishakhapatnam, India, on September 14, 1997, claiming 60 lives and causing damages to property worth over Rs 600 million, is the most recent example of the damage potential of domino effect.But, even as the domino effect has been documented since 1947, very little attention has been paid towards modeling this phenomena. In this paper we have provided a conceptual framework based on sets of appropriate models to forecast domino effects, and assess their likely magnitudes and adverse impacts, while conducting risk assessment in a chemical process industry. The utilizability of the framework has been illustrated with a case study.
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    Process Safety Progress 17 (1998) 
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    Keywords: Chemistry ; Chemical Engineering
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    Process Safety Progress 17 (1998), S. 149-154 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This article deals with fire protection for water miscible flammable liquids stored in plastic containers packaged in boxes located on pallets. A series of fire tests was conducted with palletized rack storage arrangements using in-rack sprinkler protection at various levels. The intent of the paper is to present data from this test series for these types of commodities. The paper will identify various existing water miscible flammable liquid products stored in this fashion and provide background information for protecting this type of storage as it relates to NFPA 30 Flammable and Combustible Liquids Code. The test data indicates that further research work is needed in the area of plastic containers for use with the storage of combustible and flammable liquids. Included in the paper are discussions concerning possible protection strategies and suggestions for future research which would benefit those involved in risk management of this type of commodity.
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    Process Safety Progress 17 (1998), S. 176-183 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The safest method to prevent fires and explosions of flammable mixtures in the first place. This method requires detailed knowledge of the flammability region as a function of the fuel, oxygen, and nitrogen concentrations. A triangular flammability diagram is the most useful tool to display the flammability region, and to determine if a flammable mixture is present during plant operations.This paper describes how to draw and use a flammability diagram. A procedure to estimate the flammability region using the available and sometimes limited data is discussed. The paper also shows how to use the flammability diagram with plant operations involving inerting and purging, and from bringing vessels into and out of service. A compilation of flammability diagrams for 30 materials, based on previously published data is provided.An automated apparatus for acquiring data for a flammability diagram is described. The apparatus consists of a 20-L sphere with an automated gas mixing system, a fuse-wire ignition system, and a high speed pressure measurement and data acquisition system. Data derived from the apparatus includes flammability limits, maximum pressure during combustion, and the maximum pressure rate. The effect of fuse-wire ignitor dynamics on the results is studied. A flammability diagram for methane drawn from data obtained from the apparatus, is presented.
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    Process Safety Progress 17 (1998), S. 86-97 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Regulatory issues related to material safety have made the accurate measurement and/or prediction of flash points essential. The flash point is one of the major physical properties used to determine the fire and explosion hazards of a liquid. Flash points are used by virtually all governmental entities worldwide to define “flammable” and “combustible” materials for shipping and safety regulations.A model is described here for the calculation of closed cup flash points for multicomponent, single liquid phase, mixtures. The model is based upon rigorous vapor/liquid equilibrium calculations supplemented with information about the lower flammable limits (LFL's) and heats of combustion (ΔHc's) for the mixture's constituent components. The closed cup flash points predicted with this model are typically within ± 5°C of the experimentally reported values. Such a model is useful as a means of verifying experimental data and as a tool for screening product formulations prior to experimental flash point determination. The model should considerably enhance the safety evaluation portion of the product development cycle, thus leading to shortened product time-to-market cycles. While flash points calculated with this model are in excellent agreement with experiment, experimental determination is still encouraged for critìcal safety applications.
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    Process Safety Progress 17 (1998), S. 134-137 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: National Advisory Committee's Acute Exposure Guideline Levels (AEGLs) for ammonia are critically evaluated. The technical bases for concern about AEGL-2 and AEGL-3 values derived by the committee are summarized recommendations made.
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    Process Safety Progress 17 (1998), S. 127-133 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An explosion and flash fire in a fixed bed reactor occurred at a municipal wastewater treatment plant (WWTP). Two employees were injured in the accident. The accident occurred in an ozone treatment building where ozone was used to treat odors from the offgas of the sludge concentration units. Excess ozone manually was routed to the fixed bed reactor (ozone destruct unit) where the ozone is catalytically transformed into oxygen before being discharged to the atmosphere.An investigation of the accident was conducted to determine the root cause of the explosion and flash fire and identify corrective actions which the WWTP management could undertake to prevent a recurrence. This investigation included site inspections, interview with the injured employees, sampling and analysis of various materials, an explosion dynamics analysis, and a root cause analysis.It was concluded that cooling oil from one of the ozone generation units entered the main ozone gas line due to a crack in one of the reactor's dielectric tubes. The cooling oil was vented into the ozone destruct unit when an employee opened a ball valve on the main ozone gas line. The cooling oil, essentially a saturated hydrocarbon mixture, reacted exothermically when it contacted the manganese dioxide catalyst. The exothermic reaction resulted in an explosion which propelled the access panel outwards and dispersed the catalyst pellets. A flash fire followed the explosion. The flash fire burned two employees and caused thermal damage to a nearby control panel.Although this accident was the first of its kind at this facility, this was not the first time that the ozone generator had experienced a failure of a dielectric tube. Thus, there was a significant probability that a dielectric tube failure could leak cooling oil into the main ozone gas line. This failure event could, in turn, result in another explosion and flash fire. The WWTP staff neither designed nor fabricated the ozone generator-destructor system. Therefore, it did not seem appropriate for the WWTP staff to modify the ozone system. Instead, it was recommended that the ozone destruct unit be taken out of service. The WWTP management acted on this recommendation.
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    Process Safety Progress 17 (1998), S. 171-175 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An explosion occurred in a petroleum product storage tank at a refinery. The liquid petroleum product was a heavy oil used as an asphalt extender. There were no injuries, but the cleanup was costly. The storage tank was one of several which received the product stream from a dehydration unit. The accident occurred shortly after the refinery was brought back on-line following a shutdown for schduled maintenance.This was the first incident of this kind to occur at this facility. Analysis of the process data and eyewitness observations indicated that the dehydration tower, which was supposed to be maintained at a minimum of 100°C during the shutdown, was allowed to drift below 100°C for an unknown period of time. This deviation enabled liquid water to enter the storage tank. Three operational factors contributed to the accident. Corrective actions were recommended to prevent a recurrence of a similar incident.
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    Process Safety Progress 17 (1998), S. 184-189 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dust explosions have been with us for a long time. The first record of a dust explosion occurred in Turin, Italy, on December 14, 1785 [1]. The detailed record of this event is left to us by Count Morozzo. The event took place in Mr. Giacomelli's bakery. We know from his account that the weather was unseasonably dry, that a boy who worked in the bakery was using a shovel to stir and transfer the flour to a chute from a store room to the bakery and he had a lighted lamp to work by. The rest, as the saying goes, is history. No one was killed, and the building was saved by the sagacious fact of having plenty of windows. Since that first record, of course, there have been many explosions with much loss of life and significant economic consequences.
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    Process Safety Progress 17 (1998), S. 190-195 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The RSST DIERS vent sizing methodology is revised to provide realistic design equations for reactive systems consistent with available large-scale experience. Using easy to obtain RSST data such as rate of temperature rise and rate of pressure rise excellent agreement is illustrated for hybrid, vapor and gassy reactive systems.
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    Process Safety Progress 17 (1998), S. 196-199 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: From the 1960s onwards, the chemical and oil industries developed and used a number of new safety techniques which, in time, became second nature to those who applied them. They included the use of QRA for deciding priorities, Hazop and audits for identifying problems, inherently safer design for avoiding hazards, and more thorough investigation of incidents for identifying underlying causes. However, it has not yet become second nature to remember the accidents of the past and the actions needed to prevent them happening again.I joined industry in 1944 and moved to production in 1952. Then, and for at least 15 years afterwards, safety was a non-technical subject that could be left to arts graduates and elderly foremen. There was concern that people should not be hurt - great attention was paid to the lost-time accident rate - but there was no realization, that it was a subject worthy of systematic study by experienced technologists.This view changed at the end of the 1960s. A new generation of plants had been built, operating at higher temperatures and pressures and containing larger inventories of hazardous chemicals; the result was a series of fires and explosions and a worsening fatal accident rate. Figure 1 shows the situation in ICI, at the time the UK, s largest chemical company. Other companies experienced a similar state of affairs.As a result in 1968, I was appointed one of the company's first technical safety advisers, an unusual appointment at the time for someone with my experience, and if the reason for my appointment had not been so obvious I would have wondered what I had done wrong. I and my colleagues tried to apply the same sort of systematic thinking to safety that we applied in our other professional work. We developed some new concepts and techniques and adopted others. A common feature of our ides, realized only in restrospect, was that they consisted of more than mere problem-solving techniques. Once people had got used to these new concepts and used them a few times, they began to look at a whole range of problems in a different way.
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    Process Safety Progress 17 (1998), S. W3 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
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    Process Safety Progress 17 (1998), S. 259-262 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Case histories of 65 incidents in runaway reactions and emergency relief in Taiwan were analyzed and classified into several categories according to their causes, materials involved, equipment types, reaction types, and ignition sources. The cases in reactors and storage tanks were examined in more detail owing to the higher probability or larger potential hazard in these two types of equipments. The most common consequence of the incidents are explosions, fires, and atmospheric release of toxic chemicals. The most severe case was a thermal explosion from an organic peroxide storage area which caused the death of 33 persons. Popping and direct releasing of process chemicals to the atmosphere from relieving devices cause the greatest environmental concerns to the community close to the plants. Runaway reactions in batch type reactors occur frequently due to various operational mistakes. Heat of reaction is the most frequent ignition source of runaway reactions and emergency relief.
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    Process Safety Progress 17 (1998), S. 272-277 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: EPA's Risk Management Program regulation, promulgated in June 1996 as 40 CFR Part 68 requires subject industries to submit Risk Management Plans by June 1999. This plan requires hazard assessment of the operations of a facility using worst case scenarios and alternative releases. EPA has provided an Off-site Consequence Analysis (OCA) guidance to help facilities in their hazard assessment.OxyChem will be significantly impacted by the RMP rule. This paper outlines OxyChem's general experience and its strategy in planning to comply with this rule. OxyChem's approach in the development of the scenarios required by the rule is described in this paper. Limitations involved in the use of EPA's look-up tables or a single modeling solution for conducting all of the OCA are discussed. A three tiered OCA approach is presented as a possible alternative.
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    Process Safety Progress 17 (1998), S. 209-212 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: HFC-227ea (CF3CHFCF3;1, 1, 1, 2, 3, 3, 3-heptafluoropropane) is an effective replacement for Halon 1301 in fire suppression systems, providing rapid extinguishment of flames through a combination of physical and chemical mechanisms. The vast majority of applications for HFC-227ea involve the protection of Class A hazards, which are characterized by low fuel loadings and low energy output, with fire sizes often in the range of 5-10 kW. Mid- and large-scale testing has demonstrated that HFC-227ea, at its minimum design concentration of 7.0% v/v, is effective at extinguishing fires typical of those expected to occur in electronic data processing (EDP) facilities, telecommunication facilities and anechoic chambers. The levels of HF produced following extinguishment of typical Class a fires with HFC-227ea were well below the estimated mammalian LC50 and the human Dangerous Toxic Load (DTL), and do not appear to present a threat to electronic equipment.
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    Process Safety Progress 17 (1998), S. 219-224 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Sandia National Laboratories (Sandia) has refined a process for developing inherently safer system designs based on methods used by Sandia to design detonation safety into nuclear weapons. The process was created when Sandia realized that standard engineering practices did not provide the level of safety assurance necessary for nuclear weapon operations, with their potential for catastrophic accidents. A systematic approach, which relies on mutually supportive design principles integrated through fundamental physical principles, was developed to ensure a predictably safe system response under a variety of operational and accident-based stesses. Robust, safe system designs result from this thematic approach to safety, minimizing the number of safety critical features. This safety assurance process has two profound benefits: the process avoids the need to understand or limit the ultimate intensity of off-normal environments and it avoids the requirement to analyze and test a large array of accident environment scenarios (e.g., directional threats, sequencing of environments, time races, etc) to demonstrate conformance to all safety requirements.
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    Process Safety Progress 17 (1998) 
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    Keywords: Chemistry ; Chemical Engineering
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    Process Safety Progress 17 (1998), S. 233-237 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new method is described to enhance the management of process safety risks such that the number and type of safety systems protecting against any hazard are consistently predicated upon risk. Further, that such an assignment of safety systems can be made consistent throughout an organization. This consistency is gained through standardization of qualitative risk ranking and by setting company guidelines.
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    Process Safety Progress 17 (1998), S. 243-258 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Research was carried out to develop improved protection guidelines for silane handling systems through enhanced understanding of the behavior of releases of this pyrophoric gas. The approach involved addressing three aspects of the problem: the prompt ignition behavior of silane; the reactivity characteristics of quiescent silane/air mixtures; and the rates of reaction of silane leaked into enclosures with and without explosion venting, in the presence of ventilation air flow. A first conclusion, reached from tests in a ventilated cabinet, was that, contrary to prevailing belief, the ventilation flow has no measurable effect on the prompt ignition of the release. From experiments in a 5.1-liter (311-in.3) sphere it was found that silane/air mixtures of concentrations between 1.4 and 4.1% (by volume) are explosive but stable. In this case, piloted ignition tests yielded laminar burning velocities up to 5 m/s (1000 ft/min). Mixtures between 4.5 and 38% (the maximum reached in the tests) were found to be metastable, and would undergo spontaneous ignition after a delay ranging from 15 to 120 seconds, with the shorter values corresponding to higher silane concentrations. Experiments were also performed in a 0.645-m3 (22.8-ft3) vessel both with and without explosion venting, to measure the rates of energy release associated with impulsively-started silane leaks from 1/8 and 1/4-in. (3.2 and 6.4-mm) lines. A method for the prediction of the venting requirements of partial-volume deflagrations (PVD) was evolved into a tool to quantify the pressure rise from ignition of silane leaks in enclosures. These results represent a significant step toward updating existing design recommendations which prescribe ventilation requirements that are based on outdated and, in some instances, misinterpreted data.
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    Process Safety Progress 17 (1998), S. 278-287 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Gas explosion simulators are often used as tools in process plant design. This article presents some properties of gas explosions found using the EXSIM simulation software on three offshore modules with a total of nearly 10,000 simulations. The selected results are chosen for their supposed applicability to structural design in the process industries.Generalized data are presented for the effect of gas cloud size, explosion impulse vs. explosion pressure, pressure and impulse vs. duration, the probability of a “short” explosion, loading rate, pressure-time “shape” function, and the effect of introducing louvers.
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    Adsorption 3 (1997), S. 189-195 
    ISSN: 1572-8757
    Keywords: Dubinin-Radushkevitch equation ; Dubinin-Astakhov equation ; adsorption ; micropore adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Dubinin-Radushkevitch (D-R) equation, which was originally proposed as an empirical adaptation The Polanyi adsorption potential theory, has been the fundamental equation to quantitatively describe the adsorption gases and vapors by microporous sorbents. The equation, based on the postulate that the mechanism for adsorption in micropores is that of pore-filling rather than layer-by-layer surface coverage, generally applies well to adsorption systems involving only van der Waals forces and is especially useful to describe adsorption on activated ???. The ability of the D-R equation to describe gas adsorption on porous materials has inspired many to undertake studies, both experimental and theoretical, to explain the source of the success of the D-R equation in ??? of molecular properties at the gas-solid interface. In many cases, these studies have led to extensions or modifications of the original D-R equation. Many of these attempts and the resulting extensions are reviewed and discussed here. Recently, an isotherm equation was derived for adsorption of gases and vapors on microporous ??? from statistical mechanical principles. It was shown that the D-R equation is an approximated form of this potential theory isotherm. This development is also reviewed and discussed.
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  • 72
    ISSN: 1572-882X
    Keywords: cellulase ; cottonfibres ; electron microscopy ; biopolishing ; adsorption ; colloidalgold labeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Because cellulases are finding more applications in the textile and detergent industries, their effect on cotton fibres must be evaluated. For this purpose, the action of a recombinant cellulase, endoglucanase V from the fungus Humicola insolens, has been followed by scanning electron microscopy (SEM) in classical longitudinal views as well as in cross-sections of cotton fibres. The experiments were conducted at large enzyme dilution typical of conditions where cellulases are used for biopolishing, i.e. for the removal of defects created by mechanical abrasion. Endoglucanase V appears to restrict its action to the hydrolysis of the loose fibrils created at the surface of the fibres and no indication of extensive enzyme penetration and damage to the interior of the fibres could be detected by SEM. The adsorption sites for endoglucanase V on cotton fibres were examined by transmission electron microscopy (TEM) on ultrathin cross-sections after immuno-gold labeling of the enzyme. This approach showed that the enzymes did not penetrate the fibres but remained at their surface. The use of an immuno-gold labeled cellulase provides a new way to probe the surface features of cotton fibres
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    ISSN: 1572-882X
    Keywords: biotechnology ; cellulase ; endoglucanase ; cellobiohydrolase ; adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Cellulases can be used to modify pulp fibres. For the development of biotechnical applications, a better understanding of the adsorption of cellulases onto commercial wood fibres is needed. In this work, the adsorption behaviour of purified CBH I and EG II on bleached Kraft fibres was investigated. Three variables were studied with respect to their effect on adsorption: fibre type (hardwood or softwood), fibre history (never-dried or once-dried), and ionic strength. The results showed that fibre history had the largest influence on the extent of adsorption of each enzyme. The effect of ionic strength was shown to be dependent on the enzyme and fibre type. At high ionic strength, CBH I exhibited a higher affinity for both once-dried and never-dried fibres at low enzyme concentrations; however, salt was shown to decrease the extent of adsorption at higher enzyme dosages. In contrast, salt increased the maximum adsorption of EG II, most notably on the once-dried hardwood fibres. Fibre type was also shown to affect adsorption behaviour. CBH I had a higher affinity for softwood fibres than for hardwood fibres at low enzyme concentrations. The maximum adsorption of EG II onto once-dried softwood fibres increased by 80% compared to the once-dried hardwood fibres. Interestingly, this did not correlate to in creased fibre hydrolysis.
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    AIChE Journal 43 (1997), S. 104-117 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Computational fluid dynamics methods are used to provide three-dimensional simulations of a low-density polyethylene (LDPE) autoclave reactor under normal operating conditions. For the conditions used, the reactor is not very well mixed; thus, the common model approximation of a perfectly stirred reactor is not warranted. The simulations verify the sensitive nature of the polymerization reactors and indicate a need for optimizing operating parameters.
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    AIChE Journal 43 (1997), S. 118-126 
    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 rigorous approach was developed for the simulation of the decoking of an industrial cracking furnace. A one-dimensional heterogeneous reactor model, which accounts for the interfacial gradients between the process gas and the coke surface, was used to simulate reactor coils. Both the combustion and steam gasification of the coke layer were taken into account. The reactor model for the decoking was coupled with a detailed firebox simulation model. The initial profile of the coke layer thickness, required for the decoking calculations, was obtained by a run-length simulation. The evolution with time of the temperature distribution inside the cracking coil and in the furnace was generated simultaneously, which made it possible to understand the decoking operation in detail and to predict its duration accurately.
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    AIChE Journal 43 (1997), S. 157-165 
    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 flow scheduling strategy proposed by Teymour and Ray (1989, 1996) is evaluated for a polymerization reaction conducted in a pilot-plant reactor. The reaction used is the free radical terpolymerization of styrene, α-methyl styrene, and acrylic acid monomers initiated by an organic peroxide initiator and carried out in the presence of a reactive glycol ether solvent. This strategy was tested in both single batch and sequential semibatch modes. The process was shown to produce polymer of constant molecular weight properties and composition as inferred from acid number and monomer conversion measurements. This process could be used for obtaining polymer products from a semibatch reactor that are of comparable quality to CSTR products. Results indicate success of this process at meeting this objective; however, practical considerations relating to agitation and temperature control need to be properly addressed to ensure this success.
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    AIChE Journal 43 (1997), S. 127-134 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The steady-state simulation of a cocurrently cooled autothermal fixed-bed reactor was carried out using a 2-D heterogeneous mathematical model. The ammonia synthesis was chosen as a case study. Unlike the not-autothermal cocurrent reactor, which is unconditionally stable, the autothermal cocurrent reactor shows multiple steady states within a broad range of operating conditions. This finding, not reported in the literature, is explained through the mass transport from the bottom to the top of the reactor, associated with a feedback of energy. The feedback of heat, which is inherent to autothermal reactors, leads to an ignition-extinction phenomenon similar to that found in the countercurrent configuration. The influence of different parameters on the stability of the autothermal cocurrent reactor was analyzed. The regions where steady-state multiplicity occurs were compared with those presented by the autothermal countercurrent reactor. The influence of an additional heat exchanger on the reactor stability was considered.
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    AIChE Journal 43 (1997), S. 277-280 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 43 (1997), S. 265-267 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 43 (1997), S. 268-272 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 81
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    AIChE Journal 43 (1997), S. 339-344 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental investigation was conducted to determine the boiling heat-transfer characteristics in a thermosyphon condenser-reboiler of air-separation plants. The test section was a plate-fin heat exchanger of practical size of 0.106 m width and 2.56 m length. The testing fluid was nitrogen. Experiments were carried out within a range of pressure from 150 to 300 kPa, submergence from 1.95 to 2.80 m, and heat flux up to 11 kW/m2 under constant wall-temperature condition. The liquid superheat at the onset of boiling was rather significant. The boiling heat-transfer coefficients obtained agreed well with Chen's correlation modified by Colburn's J factor within a mean deviation of 9.3%.
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  • 82
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    AIChE Journal 43 (1997) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 83
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    AIChE Journal 43 (1997), S. 440-447 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The concept of robust design involves identification of design settings that make the product performance less sensitive to the effects of seasonal and environmental variations. This concept is discussed in this article in the context of batch distillation column design with feed stock variations, and internal and external uncertainties. Stochastic optimization methods provide a general approach to robust/parameter design as compared to conventional techniques. However, the computational burden of these approaches can be extreme and depends on the sample size used for characterizing the parametric variations and uncertainties. A novel sampling technique is presented that generates and inverts the Hammersley points (an optimal design for placing n points uniformly on a k-dimensional cube) to provide a representative sample for multivariate probability distributions. The example of robust batch-distillation column design illustrates that the new sampling technique offers significant computational savings and better accuracy.
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  • 84
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    AIChE Journal 43 (1997), S. 33-44 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Equations were derived that describe the dynamics of cake growth in cake filtration, and methods for their solutions were developed. In deriving the equations, the moving boundary nature of the cake formation process and the effect of fine particle retention were considered. It was shown that fine particle retention may contribute significantly to the decrease of cake permeability and thus alters the performance of cake filtration even if the amount of fine particles involved is small. Through numerical examples, it was also demonstrated that fine particle retention in filter cakes may cause serious errors in determining the constitutive relationships from filter test data.
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  • 85
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    AIChE Journal 43 (1997), S. 45-57 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Fundamental characteristics of liquid-solid fluidization at high pressures (up to 21 MPa) and moderate temperatures (up to 89°C) are investigated. Properties under study include minimum fluidization velocity (umf), bed voidage at minimum fluidization, and bed expansion. Devices for in-situ measurements of physical properties of the liquid in the bed are developed, and measurements are carried out to quantify the pressure and temperature effects on the fluidization behavior. The results indicate that under high pressures and moderate temperatures, liquid-solid fluidization behavior is affected significantly by the variation of liquid density and viscosity with pressure. As the pressure increases, the liquid viscosity and density increase, yielding an increased drag force and buoyancy force on the particles, and hence a decreasing umf and an increasing bed expansion for a given liquid flow rate. An increase in temperature has an opposite effect on the physical properties of the liquid, increasing umf and decreasing the bed expansion for a given liquid flow rate. Various correlations proposed in the literature for umf and bed expansion, including those by Richardson and Zaki (1954) and Chitester et al. (1984), are applicable to high-pressure and high-temperature conditions when proper account is made of the liquid physical properties under bed operating conditions.
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  • 86
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    AIChE Journal 43 (1997), S. 58-63 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Asymptotic power series solutions for the mass-transfer enhancement factor for absorption of a gas component into a liquid where it undergoes irreversible instantaneous chemical reaction(s) with one and two liquid-phase reactants are developed in this work. The Padé technique is used to extend the region of applicability (accelerate the convergence) of the four-term asymptotic power series solutions. The resulting modified asymptotic expressions for the enhancement factor show excellent accuracy over a wide range and can be used to predict enhancement factors as low as 2 with an error of about 5% compared to the exact numerical solution. Predictions of these new asymptotic solutions are compared with experimental absorption data for H2S absorption into aqueous methyldiethanolamine and H2S absorption into aqueous mixtures of methyldiethanolamine and diethanolamine obtained in a laminar-jet absorber. The absolute mean deviations of the predictions from the experimental absorption data for the single and mixed amine solutions were 4.6% and 2.4%, respectively.
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  • 87
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    AIChE Journal 43 (1997), S. 166-172 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: When a trickle-bed reactor (TBR) is operated periodically, the bed is fed with liquid on and off, while the gas phase passes continuously. Rates and conversions could be higher than those corresponding to the steady-state operation. In the “dry cycles” the heat generated by the reaction can drive the vaporization of the liquid phase, and a much more rapid “gas phase” reaction may occur. There is a trade-off between the potential for hot-spot formation and the fact that overall rates are higher during cycling. A qualitative understanding of the phase transition in TBRs is obtained by a simple phenomenological model that takes into account different transport and reaction mechanisms occurring in a catalytic particle under different cycling conditions. A mathematical model is used to predict results.
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  • 88
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    AIChE Journal 43 (1997), S. 180-195 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Theoretical and engineering models for the thermodynamic properties of strong electrolyte solutions have advanced significantly since 1985. This progress is notable in the ability to calculate selected properties of single and mixed strong electrolyte solutions over a wide range of temperatures and compositions, including effects of various nonelectrolytes, solvents and supercritical components. Theoretical studies have begun to consider more realistic fundamental interactions between various components in these systems. There have been several successful conversions of theories based on the mean spherical approximation and perturbation methods into engineering equations, without large numbers of empirical parameters. Other theoretical models seem almost ready for application to real systems. The capability to estimate a wide variety of thermodynamic properties accurately with a consistent set of equations and a small number of adjustable parameters has been achieved by several groups over limited temperature and composition ranges. Much work remains to be done, however, to understand completely the interplay and relative importance of various contributing energy effects.
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  • 89
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    AIChE Journal 43 (1997), S. 212-217 
    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 NpT + test-particle method for the calculation of vapor-liquid equilibria by molecular simulations is extended to ternary mixtures. It is applied to the system methane + ethane + carbon dioxide, for which all binary molecular interaction models are available from previous work. Methane is described as one-center Lennard-Jones fluid, ethane as two-center Lennard-Jones fluid, and carbon dioxide as two-center Lennard-Jones plus point quadrupole fluid. The unlike interactions are treated in the same way as the binary mixtures, using two parameters for each binary interaction. No ternary parameters are introduced. Vapor-liquid phase equilibria are calculated for the ternary mixture at the following temperature-pressure pairs: 233.15 K - 2 MPa; 250.5 K - 2 MPa; and 250.5 K - 3.04 MPa. Comparison of the simulation data with experimental and equation-of-state results shows excellent agreement. Bubble and dew densities are also reported.
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  • 90
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    AIChE Journal 43 (1997), S. 232-242 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An efficient and economical low-pressure liquid chromatography process has been developed for paclitaxel recovery and purification directly from plant-tissue culture (PTC) broth. PTC broth is first diluted with ethanol to ensure padlitaxel dissolution and then passed through a column packed with a high-capacity polystyrene divinyl-benzene sorbent. A step increase in ethanol concentration in the mobile phase (ethanol:water) is used to concentrate and compress the taxane bands to as high as 29-fold of influent concentrations (about 1 mg/L). A recycle technique is then used to separate the concentrated paclitaxel band from other taxane bands, achieving 95% purity with more than 90% recovery and 99% purity with more than 80% recovery. In this process, the same low-pressure columns are used to capture, concentrate and purify paclitaxel. Theoretical predictions agree closely with the stepwise elution and recycle chromatography data. After validation, simulations are used to explore various design and operating alternatives. Analysis of the alternatives shows that the process cost can be further reduced by using higher feed concentration, larger loading volume, smaller particle size, and optimal gradient and recycle strategies.
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  • 91
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    AIChE Journal 43 (1997), S. 218-231 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: When polymers are added to a solution containing proteins, the protein may deposit as an amorphous precipitate or as crystals. Experimental evidence indicates that from a thermodynamic viewpoint, an amorphous precipitate should be treated as a liquid phase dense in the protein and crystals as true solids. To understand the conditions under which protein precipitation or crystallization may occur, Gibbs-ensemble Monte Carlo simulation and Gibbs-Duhem integration techniques are used to calculate the liquid-liquid and liquid-solid phase boundaries for protein precipitation induced by polymers. In these simulations, the system is modeled using the pseudo-one-component approximation with an appropriate potential of mean force. The critical point for fluid-fluid phase equilibrium disappears as the attractive part of the mean-force potential becomes very short ranged. The accuracy of the second-order Barker and Henderson perturbation theory is examined by comparing the phase diagram predicted using this method with the simulation results. Perturbation theory is able to predict the general trends observed in the simulations but not with quantitative accuracy. Perturbation theory is then used to examine a broader range of conditions for protein deposition.
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  • 92
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    AIChE Journal 43 (1997), S. 260-262 
    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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  • 93
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    AIChE Journal 43 (1997), S. 935-945 
    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 simulated moving bed (SMB) was operated for the separation of mixtures of 2-phenyl ethanol and 3-phenyl-1-propanol on columns packed with Zorbax C18 bonded silica, using a 60:40 (v/v) solution of methanol and water as the mobile phase. Series of four or eight columns were used. The experiments were carried out with low concentration mixtures, that is, under linear conditions. Band profiles of both compounds eluted from one of the columns during successive periods after steady state had been reached were recorded, as were the concentration histories at the extract and raffinate ports. These experimental results are compared to those predicted by two models: the linear ideal and the linear equilibrium-dispersive models of chromatography, applied to the SMB separator. These two models give excellent agreement between the experimental profiles and those calculated with the model. As expected, the profiles predicted by the ideal and the equilibrium-dispersive models differ only by the lack of dispersion in the profiles given by the former. The latter model is demonstrated to be a solid, reliable tool for further studies of the SMB design and optimization.
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To study the influence of particle concentration on the hydrodynamics of bubble-column slurry reactors operating in the heterogeneous flow regime, experiments were carried out in 0.10, 0.19, and 0.38-m-dia. columns using paraffinic oil as the liquid phase and slurry concentrations of up to 36 vol. %. To interpret experimental results a generalization of the “two-phase” model for gas-solid fluid beds was used to describe bubble hydrodynamics. The two phase identified are: a dilute phase consisting of fast-rising large bubbles that traverse the column virtually in plug flow and a dense phase that is identified with the liquid phase along with solid particles and entrained small bubbles. The dense phase suffers backmixing considerably. Dynamic gas disengagement was experimented in the heterogeneous flow regime to determine the gas voidage in dilute and dense phases. Experimental data show that increasing the solid concentration decreases the total gas holdup significantly, but the influence on the dilute-phase gas holdup is small. The dense-phase gas voidage significantly decreases gas holdup due to enhanced coalescene of small bubbles resulting from introduction of particles. The dense-phase gas voidage is practically independent of the column diameter. The dilute-phase gas holdup, on the other hand, decreases with increasing column diameter, and this dependence could be described adequately with a slight modification of the correlation of Krishna and Ellenberger developed for gas-liquid systems.
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  • 95
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    AIChE Journal 43 (1997), S. 475-485 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Strong intraparticle diffusion resistance was observed and the apparent effectiveness factors were measured for the hydrogenation of 3-hydroxypropanal (HPA) to 1,3-propanediol (PD) over Ni/SiO2/Al2O3 catalyst pellets at 45 to 80°C and 2.60 to 5.15 MPa in a stirred reactor with a spinning basket. A mathematical model was proposed to describe the intraparticle diffusion and to estimate the effective diffusion coefficients of HPA, PD and hydrogen under reaction conditions by a maximum likelihood function of the apparent effectiveness factors of HPA and PD. The calculated concentration distributions of HPA, PD and hydrogen in catalyst particles reveal an excess of hydrogen at 80°C and higher temperatures, but an excess of HPA at 45°C. It results in a weak dependence of the consumption formation rate of HPA and PD on the partial pressure of hydrogen at high temperature.
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  • 96
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    AIChE Journal 43 (1997), S. 631-644 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Electrophoresis of a solute through a column in which its transport is governed by the convection - diffusion equation is described. Approximate solutions to the convection - diffusion equation in the limit of small diffusion are developed using perturbation methods. The diffusion coefficient and velocity are assumed to be functions of space and time such that both undergo a sudden change from one constant value to another within a thin transition zone that itself translates with a constant velocity. Two cases are considered: (1) the thickness ∊f of the transition zone is negligible compared to the diffusional length scale, so the zone may be treated as a singular boundary across which the diffusion constant and velocity suffer discontinuous changes; (2) the transition zone is considerably wider than the diffusional length scale, so the diffusion coefficient and velocity, although sharply varying, are smooth functions of position and time. A systematic perturbation expansion of the concentration distribution is presented for case 1 in terms of the small parameter ∊ = 1/Pe. A lowest order approximation is given for case 2. A suitably configured system analyzed here can lead to progressive accumulation, or focusing, of the transported solute. The degree of focusing in case 1 scales with ∊-1, whereas in case 2 it scales with (∊f∊)-1/2, and thus increases much more weakly with increasing Pe. A separation based on this concept requires development of materials and devices that allow dynamic tuning of the mass-transport properties of a medium. This would make it possible to achieve progressive focusing and separation of solutes, such as proteins and DNA fragments, in electrophoretic media with an unprecedented degree of control.
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  • 97
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    AIChE Journal 43 (1997), S. 681-692 
    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 influence on drying selectivity of the continuous-contact mode between a solid wetted with ternary mixtures and a gas stream was theoretically studied. The liquid mixtures, ethanol-isopropanol-water and water-ethanol-acetone, were used. A mathematical model describing a gas-phase-controlled process was developed, and the influence of the process variables was studied by simulations. In addition to the inlet composition of the moisture and temperature of the solid, gas composition has the most important effect on selectivity. Small changes of gas composition, either imposed or spontaneous, may modify completely the process trajectory. The extent of these effects depends on the ratio between the flow rates of inlet gas and liquid contained in the solid. Because of their effects on the evolution of temperature and composition, the operating pressure and energy sources other than convection are also useful in controlling the selectivity. Since all these variables determine the composition of the remaining liquid and thereby product quality, their influence should be predictable. The model may be a valuable tool for exploring the process, provided that drying is gas-phase-controlled.
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    AIChE Journal 43 (1997), S. 844-846 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 43 (1997), S. 577-587 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Complex mixing flows and mixing parameters are calculated to evaluate mixing quality on the basis of kinematic parameters together with a statistical analysis. The results allow for a comparative evaluation in terms of geometry and flow parameters. The evaluation is limited to two-dimensional flows with moving boundaries in periodic motion such as the flow in the cross section of a twin-cam mixer. The finite-element calculation requires a remeshing procedure for every time step with special techniques to upgrade mixing variables from one time step to the next. The relative mixing quality of single cam and co: or counterrotating cam devices are compared by evaluating segregation scale, length stretch, and efficiency. The numerical results exhibit a good correspondence with their experimental counterpart.
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    AIChE Journal 43 (1997), S. 615-624 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Resonant power absorption is an important phenomenon during microwave heating. The resonances that occur when plane electromagnetic waves are incident on infinitely long cylinders and slabs are investigated as a function of sample dimensions. For cylinders two kinds of incident waves are studied: TMz when the electric field is oriented along the axis of the cylinder and TEz when the magnetic field is oriented along the axis. At a resonant condition the overage power absorbed by the sample is a local maximum. Due to attenuation within the sample the resonances decrease in intensity as the sample size increases. Using the dielectric properties of water, resonances are found to be a function of the ratio of the sample dimension to the wavelength of radiation, λs, in the sample. For slabs of thickness L and integer values of n, resonances occurred at L/λs = 0.5n; for cylinders of diameter D, resonances occurred at D/λs = 0.5n - 0.257. The generality of these relations to predict resonances in other food samples are shown using existing dielectric data. Resonances in cylinders for both polarizations occurred at similar radii. However, the radius at which the first resonance occurred for the TMz case was absent in the TEz case.
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