Hollow fiber enzymic reactors for a two substrate process: analytical modeling and numerical simulations

The use of immobilized enzyme reactors in biotechnology and biomedicine is rapidly expanding. This study concentrates on hollow-fiber (HF) enzymic reactors for continuous, single-pass operation. The enzyme, in a soluble form, is physically confined within the shell section of the reactor and the substrate solution flows through the lumen section of it. We consider here a two-substrate reaction proceeding via the Ping-Pong mechanism, with substrates and reaction products diffusing through the fiber wall. The developed analytical model enables to calculate the expected conversion as a function of the volumetric flow rate, kinetic constants, diffusion coefficients, geometric dimensions of the reactor, the flow regimen in the apparatus and substrates concentrations. The model equations are solved by a numerical procedure and the system performance is simulated. Depending on the operation conditions employed, the reactor is controlled by kinetic processes, diffusion processes, or both.     

Solvent-induced crystallization of syndiotactic polystyrene in different liquids—sorption and diffusion phenomena

Transport properties of different liquids inducing crystallization in syndiotactic polystyrene (sPS) were investigated at 25°C. The weight uptake kinetics in the different liquids imply Fickian behaviour, with the exclusion of n-hexane and cyclohexane for which the weight uptake starts after an induction time. The equilibrium concentration of the different liquids in sPS is a function of the solubility parameter and shows a maximum with respect to chloroform, indicating a maximum in the polymer-solvent interaction. The swollen samples are birefringent but appear substantially amorphous on the basis of the X-ray diffractograms. After drying a well developed crystalline order appears, and the diffractograms indicate the presence of solvated structures, characterized by chains in helical conformation.     

Sorption/desorption,diffusion, and swelling characteristics of geomembranes in the presence of halo‐organic liquids

Sorption/desorption results of halogen‐containing liquids into high‐density polyethylene, linear low‐density polyethylene, very low‐density polyethylene, and polypropylene geomembranes are presented at 25, 50, and 70°C. Sorption results are obtained by a gravimetric method, and diffusion coefficients have been calculated by using Fick's equation from the initial linear portions of the sorption/desorption curves. Swelling of the geomembranes was studied from a measurement of the increase in volume, thickness, and diameter. From a temperature dependence of sorption and diffusion coefficients, the Arrhenius parameters have been calculated. Liquid concentration profiles have been computed using Fick's equation for the appropriate initial and boundary conditions. The results of this study may have relevance in selecting the suitable geomembrane for a specific application in hazardous waste chemical ponds and other similar situations.     

Study on diffusion and flow of benzene, n-hexane and CCl4 in activated carbon by a differential permeation method

In this paper the diffusion and flow of carbon tetrachloride, benzene and n-hexane through a commercial activated carbon is studied by a differential permeation method. The range of pressure is covered from very low pressure to a pressure range where significant capillary condensation occurs. Helium as a non-adsorbing gas is used to determine the characteristics of the porous medium. For adsorbing gases and vapors, the motion of adsorbed molecules in small pores gives rise to a sharp increase in permeability at very low pressures. The interplay between a decreasing behavior in permeability due to the saturation of small pores with adsorbed molecules and an increasing behavior due to viscous flow in larger pores with pressure could lead to a minimum in the plot of total permeability versus pressure. This phenomenon is observed for n-hexane at 30°C. At relative pressure of 0.1-0.8 where the gaseous viscous flow dominates, the permeability is a linear function of pressure. Since activated carbon has a wide pore size distribution, the mobility mechanism of these adsorbed molecules is different from pore to pore. In very small pores where adsorbate molecules fill the pore the permeability decreases with an increase in pressure, while in intermediate pores the permeability of such transport increases with pressure due to the increasing build-up of layers of adsorbed molecules. For even larger pores, the transport is mostly due to diffusion and flow of free molecules, which gives rise to linear permeability with respect to pressure.     

Sorption and diffusion of aldehydes and ketones through castor oil-based interpenetrating polymer networks of PU–PS

Sorption and diffusion of some aldehydes and ketones into interpenetrating polymer networks (IPNs) of polyurethane–polystyrene (PU–PS) have been investigated in the temperature interval of 25–60°C. Transport data were found to be affected by the nature of the interacting solvent molecule rather than its size. The diffusion coefficient of ketones range from 9.2 × 10⁻⁸ to 645 × 10⁻⁸ cm²/s and for aldehyde from 11.5 × 10⁻⁸ to 154.5 × 10⁻⁸ cm²/s. For all solvents, the polymer remained intact. From the temperature dependence of sorption data, the Arrhenius activation parameter and the thermodynamic parameter, such as entropy and enthalpy for the process of equilibrium sorption, have been estimated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2047–2055, 1998     

Effects of material parameters on the diffusion and sorption properties of wood‐flour/polypropylene composites

Composites of wood in a thermoplastic matrix (wood–plastic composites) are considered a low maintenance solution to using wood in outdoor applications. Knowledge of moisture uptake and transport properties would be useful in estimating moisture‐related effects such as fungal attack and loss of mechanical strength. Our objectives were to determine how material parameters and their interactions affect the moisture uptake and transport properties of injection‐molded composites of wood‐flour and polypropylene and to compare two different methods of measuring moisture uptake and transport. A two‐level, full‐factorial design was used to investigate the effects and interactions of wood‐flour content, wood‐flour particle size, coupling agent, and surface removal on moisture uptake and transport of the composites. Sorption and diffusion experiments were performed at 20°C and 65 or 85% relative humidity as well as in water, and diffusion coefficients were determined. The wood‐flour content had the largest influence of all parameters on moisture uptake and transport properties. Many significant interactions between the variables were also found. The interaction between wood‐flour content and surface treatment was often the largest. The diffusion coefficients derived from the diffusion experiments were different from those derived from the sorption experiments, suggesting that different mechanisms occur. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 752–763, 2007     

Kinetic and isotherm studies of the adsorption of Acid Blue 92 using a low-cost non-conventional activated carbon

Adsorbents prepared from waste plants for the treatment of dyeing effluents have high significance in environmental sustainability. In this research, an attempt is made to analyze the applicability of activated carbon prepared from Euphorbia antiquorum L wood by H₃PO₄ activation method for the removal of Acid Blue 92 dye. Various kinetic models were used for the analysis of adsorption kinetics and pseudo second-order model fits well for the selected adsorbent-adsorbate system. The moderate rate of dye uptake indicates that the rate-determining step could be physisorption in nature. Langmuir, Freundlich and Dubinin-Raduskevich isotherm models were applied for the analysis of isotherm data. The positive enthalpy of adsorption substantiates that the adsorption process is endothermic in nature.     

Sorption and diffusion of volatile organic compounds in fluoroalkyl methacrylate‐grafted PDMS membrane

Pervaporation is known as an excellent method for the purification of contaminated water, the extraction of aroma compounds, etc., and has been widely studied. The prediction of permeation is important for treatment, extraction, and quantitative analysis. To predict permeation, a solution–diffusion mechanism is proposed. The octanol–water partition coefficient (Pow) has been generally used in expressing hydrophobicity. The hydrophobicity, Pow, is closely related to the solubility of organic compounds. Also, the molecular volume is closely related to the diffusion of organic compounds. In this study, we improved polydimethylsiloxane (PDMS) membranes by plasma grafting of fluoroalkyl methacrylates (FALMA) to enhance the affinity of PDMS to volatile organic compounds (VOCs). Furthermore, we investigated the pervaporation through the plasma‐grafted PDMS membrane and the PDMS membrane and the solution–diffusion mechanism of various VOCs. The permselectivity of tetrachloroethylene (PCE) and toluene determined by the sorption and the diffusion characteristics permeating in the membrane was high. Because the molecular volume of the VOCs is greated than that of water and the permeates quickly penetrate in rubbery membranes like PDMS, permselectivity was not affected by the diffussivity. Solubility significantly affected the permselectibity during pervaporation through a hydrophobic rubbery membrane. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 773–783, 2000     

Experimental and simulation studies on molecular transport of substituted monocyclic aromatic liquids into fluoropolymer sheet membranes: Liquid structure–diffusion, –sorption,and –permeation relationships

The present study reports an investigation on the molecular transport of 10 monocyclic aromatic liquids (benzene, chlorobenzene, 1,2‐dichlorobenzene, bromobenzene, toluene, p‐xylene, trimethylbenzene, ethylbenzene, methoxybenzene, and ethoxybenzene) at 40 and 50°C through sheet polymeric membranes (FLS‐2650) using a sorption gravimetric technique. Diffusion and permeation coefficients of these liquids were calculated from the sorption data using Fick's diffusion equation. Sorption results were analyzed typically in the case of benzene and chlorobenzene to compute the concentration profiles at different depths along the thickness direction of the sheet membranes and at different time intervals by solving the Fick's equation under appropriate boundary conditions, based on the numerical simulation method developed in “C” language using a finite‐difference method. Transport results were analyzed to establish the relationships between the penetrating liquid structures with diffusion, permeation, and sorption data. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 991–996, 2004     

In situ and ex situ FTIR–ATR and Raman microscopic studies of organosilane hydrolysis and the effect of hydrolysis on silane diffusion through a polymeric film

We report combined FTIR–ATR and Raman microscopic studies of the distribution and redistribution of three different silane adhesion promoters in thin (10–20 μm) PVC films deposited on a Si/SiO₂/SiOH substrate (a “model” glass surface). It has been shown that the different functionalized silanes diffuse at different rates through the polymer (at 70°C) and therefore have different distributions at the polymer/glass interface. The differences in behavior have been rationalized in terms of their respective abilities to hydrolyze and condense, under the different humidity and temperature conditions used. As the level of humidity rises there is evidence that the diffusion rate (measured using a dual‐mode sorption model) decreases as a result of hydrolysis and condensation in the polymer films. The data are of importance as a direct measure of the relation between humidity levels and the adhesive action of a silane promoter at polymer/glass interfaces. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2016–2026, 2001     

Influence of flexible oligo(tetrafluoroethene) segment on the sorption and diffusion of carbon dioxide in poly(amide‐imide) membranes

Molecular simulations have been used to study the sorption and diffusion properties of carbon dioxide in a series of poly (amide‐imide) (PAI) membranes containing oligo(tetrafluoroethene) segment with various numbers (n = 0, 1, 2, 3, and 4) of tetrafluoroethene units. The solubility and self‐diffusion coefficients were computed by the Grand Canonical Monte Carlo (GCMC) method and molecular dynamics (MD) simulations respectively. It was found that increasing the fluorine content of the polymer membrane reduced the associated glass transition temperature (T_g) and led to an increase in diffusion coefficient of carbon dioxide. Results indicate that penetrant molecule's diffusion coefficient is strongly dependent on chain mobility. It is also noticed that the radial distribution functions (RDFs) are inconsistent with the d‐spacings of PAIs calculated form X‐ray data. This is also thought to be tied to the number of degrees of freedom of the chain. Finally, this study gives a useful insight into how PAIs with high fluorine content can be tailored with a high permeability to carbon dioxide. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Sorption,diffusion, and swelling characteristics of sodium alginate and its blend membranes with poly(vinyl alcohol) in water–acetic acid mixtures

Sorption, diffusion, and swelling characteristics of sodium alginate and its blend membranes with poly(vinyl alcohol) were investigated for water–acetic acid mixtures by using a gravimetric method at 30, 40, and 50°C. The membranes were characterized by X‐ray diffraction and Fourier transform infrared techniques. Concentration‐independent diffusion coefficients were obtained by applying Fick's relationship before completion of equilibrium sorption. Permeation coefficients were calculated from sorption and diffusion coefficients. Concentration profiles of liquids were computed considering the sheet geometry for the membrane by solving Fick's equation under suitable boundary conditions. Arrhenius activation parameters were computed for the transport processes. Experimental results and calculated quantities were discussed to understand membrane–solvent interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1139–1150, 2004     

Optimization of particle size,dispersity, and conductivity of 8 mol% Y2O3 doped tetragonal zirconia polycrystalline nanopowder prepared by modified sol-gel method via activated carbon absorption

8 mol% Y₂O₃ doped tetragonal zirconia polycrystalline (8Y-TZP) ceramic nanopowders were synthesized via a novel modified sol-gel method employing zirconium carbonate basic as zirconium resources. The activated carbon as a dispersant was added to the precursor solution during the formation of the sol. The phase behavior, thermal decomposition, microstructure morphology, and electrochemical performance of nanopowders with the addition of activated carbons were investigated by X-ray diffraction (XRD), differential thermal analysis (DTA), scanning electron microscopy (SEM), particles size distribution, and electrochemical impedance spectroscopy analysis (EIS). After adding the activated carbon, the average crystallite size of 8Y-TZP nanopowders decreased from about 53.16–33.51 nm when calcined at 900 ℃, and the 8Y-TZP nanopowders were produced loosely agglomerated. Meanwhile, compacts prepared by pressing the as-obtained 8Y-TZP nanopowders sintered to 98.8% relative density at 1600 ℃ and exhibited an average grain size of 0.89 µm, which brought a positive effect on ionic conductivity (0.079 S·cm^?1).     

Swelling and diffusion studies of poly(N‐isopropylacrylamide/itaconic acid) copolymeric hydrogels in water and aqueous solutions of drugs

N‐Isopropylacrylamide/itaconic acid hydrogels (NIPAAm/IA) containing different amounts of itaconic acid prepared by irradiating with γ‐radiation were used in experiments on swelling and diffusion of the model drugs methylene blue, lidocaine, and sildenafil citrate (VIAGRA). The NIPAAm/IA hydrogels containing 0–3 mol % itaconic acid irradiated at 48 kGy has been used for swelling and diffusion studies in water and aqueous solutions containing the above‐mentioned model drugs. For these hydrogels, swelling studies indicated that swelling increased with the following order: water > lidocaine > methylene blue > VIAGRA. Diffusions of water and the drugs within hydrogels were found to be non‐Fickian in character. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 911–915, 2004     

Silkworms’ feces-based activated carbons as cheap adsorbents for removal of cadmium and methylene blue from aqueous solutions

Activated carbon samples, ACs, were obtained from silkworms’ feces via chemical activation method. Many activating agents including the new ones KCl, CrCl₃ and TiCl₄ were compared. Acidic and basic oxidic groups in addition to aromatic tertiary and secondary amines have been detected on the surface of produced ACs. Furthermore, microporous solids furnishing high internal specific surface area, ranging between 1000 and 2000 m²/g, and total pore volume up to 0.85 cm³/g were obtained. TiCl₄ resulted in the solid possessing the highest area and pore volume. The obtained solids showed high efficiency in removing methylene blue and cadmium from their aqueous solutions. Adsorption capacity of sample AC/TiCl₄ is 461 mg/g of MB at pH = 10, and 62.6 mg/g of Cd²⁺ at pH = 8. The nature of the formed microporous texture and the prevailing surface oxidic groups are the main controlling parameters for the observed high efficiency toward both adsorbates.     

Mixing from Fickian diffusion and natural convection in binary non‐equilibrium fluid phases

A two‐dimensional (2‐D) model that describes mass transport between non equilibrium gas and liquid phases of a binary non polar mixture in a closed system of fixed volume and temperature is presented. Diffusion, convective mass transport due to compressibility and non ideality, and the motion of the interface upon evaporation and dissolution are accounted. Natural convection in both phases is incorporated, which allows to study the effect of density increase in the liquid phase from gas dissolution. The Peng‐Robinson equation of state is used to calculate the densities and the fugacities needed to find the interfacial composition consistent with local chemical equilibrium. The results obtained with a one‐dimensional model was compared to our 2‐D results, showing that natural convection influences the mixing time drastically. In the liquid bulk phase, convective flux is much higher than diffusive flux. Across the interface, diffusive flux is, however, the dominating flux, which allows accurate measurement of diffusion coefficients at high pressure in 2‐D domains. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Sorption/diffusion of aqueous mixtures of 1,4‐dioxane/tetrahydrofuran through blend membranes of poly(vinyl alcohol) and sodium alginate: Their compatibility and pervaporation separation studies

Blend membranes of poly(vinyl alcohol) (PVA) and sodium alginate (NaAlg) were prepared by solution casting and crosslinked with glutaraldehyde (GA). Polymer blend compatibility was studied in water by measuring solution viscosity at 30°C. From the viscosity data, interaction parameters were determined to find the blend compatibility. Thickness of the membranes ranged between 35 and 40 μm. Circular disc‐shaped samples were cut from the thin membranes to perform gravimetric sorption experiments in water + 1,4‐dioxane and water + tetrahydrofuran mixtures at 30°C. Diffusion coefficients were calculated using Fick's equation. Concentration profiles of liquids were computed by solving Fick's equation under suitable boundary conditions. Diffusion coefficients show a dependence on the composition of the blends as well as composition of binary mixtures. A correlation was attempted between concentration profiles and diffusion coefficients of the transporting liquids. Degree of swelling and sorption coefficients were calculated from the gravimetric sorption data. Sorption kinetics was studied using an empirical equation to understand the nature of sorption–diffusion anomalies. Membrane selectivity for water + 1,4‐dioxane and water + tetrahydrofuran mixtures were calculated from the pervaporation experiments. A correlation between sorption and membrane selectivity was attempted. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 178–188, 2005     

Theoretical analysis and experimental study on SO2 adsorption onto pistachio‐nut‐shell activated carbon

The adsorption study of SO₂ onto the activated carbon prepared from pistachio‐nut shell was studied theoretically and experimentally. A single‐particle sorption model known as concentration‐dependent surface diffusivity micropore, surface and macropore diffusion control model incorporating micropore, macropore and surface diffusions, together with a nonlinear isotherm at the micropore mouth, has been derived and solved by a finite difference method. The effects of different types of nonlinear isotherms and concentration dependent surface diffusivities have been thoroughly studied. The effects of adsorbate concentration and temperature on adsorption were studied experimentally. Good agreement was found between the model predictions and the experimental results. The value of the tortuosity factor and the extracted diffusion coefficients obtained are consistent with their corresponding values reported. © 2008 American Institute of Chemical Engineers AIChE J 2009     

Evaluation of polyaromatic hydrocarbon removal from aqueous solutions using activated carbon and hyper‐crosslinked polymer (Macronet MN200)

BACKGROUND: Sorption of polycyclic aromatic hydrocarbons (PAHs) on activated carbon and the Macronet polymeric sorbent MN200 was investigated to determine the effectiveness of each sorbent for removal of pollutants from aqueous solution and their possible use as sorbent materials for groundwater. Experiments were carried out to determine the loading capacities of a family of PAHs (acenaphthene, anthracene, fluoranthene, fluorene, naphthalene and pyrene). RESULTS: Activated carbon was the more effective sorbent, with maximum loadings of PAHs between 90 and 230 g kg^?1, while MN200 resin showed values of 25–160 g kg^?1. Loading isotherms based on the Langmuir, Freundlich and Redlich–Peterson models were determined. The hydrophobic character of the pollutants appeared as an important parameter related to the sorption process. Equilibrium and kinetic parameters were used to determine the retardation factors for each PAH. CONCLUSION: The calculated values for the simulation of barrier thickness using both sorbents, taking into account EU requirements for PAHs in groundwater effluent, were perfectly reasonable as a first estimate. The better kinetic properties of MN200 are evident in lower hydraulic residence times and consequently in a lower barrier thickness. Copyright © 2008 Society of Chemical Industry