Effect of particulate matter on mass transfer through microporous hollow fiber membranes

Inner walls of microporous hollow fibers were exposed to a particle-laden gas stream for 80 h. The gas stream contained 0.25-μm diameter particles, typical of fly ash particles found in flue gas streams, that were generated by a wet-particle technique. During the deposition period, the pressure drop across the length of the fibers increased slowly at the start of the experiment and then more rapidly later, reaching 100 in. of water in 30 h. Particle interception by fibers at the feed inlet may be the chief reason for the rise in the pressure drop. The mass transfer coefficient (MTC) for SO₂ absorption into water dropped by 20% during this time. Particles coating the inside fiber walls may be the chief reason for the reduction in MTC. While the pressure drop could be reversed to its original value by the backflow of a pressurized air-jet, the MTC could not.     

CFD modeling for flow and mass transfer in spacer-obstructed membrane feed channels

The effect of spacer geometry on fluid dynamics and mass transfer in feed channels of spiral wound membranes has been investigated. Three-dimensional computational fluid dynamics (CFD) simulations reveal significant influence of spacer geometric parameters such as filament spacing, thickness and flow attack angle on wall shear rates and mass transfer coefficients. The spacers with filaments in axial and transverse direction induce higher shear stresses at the top membrane surface when compared to the bottom; the mass transfer rates are almost equal. The distribution of mass transfer coefficients become uniform when the spacing between axial filaments is increased or transverse filament thickness is decreased. For spacers with filaments inclined to the channel axis, the flow structure depends on spacing and flow attack angle. The fluid follows a zigzag path when spacing is greater while it begins to line-up with the filaments when spacing is reduced or flow attack angle is increased. The flow when aligned with the filaments increases the wall shear stress but confines the region of higher mass transfer coefficient values to a narrower portion. The zigzag flow movement increases these values on a major portion of membrane surface which enhances the mass transfer rates.     

Mass transfer characteristics for VOC permeation through flat sheet porous and composite membranes: The impact of the different membrane layers on the overall membrane resistance

In this paper, the mass transfer coefficients for trichloroethylene (TCE), toluene (TOL) and dimethyl sulfide (DMS) are experimentally determined for different porous and composite membranes. For polypropylene/polyvinylidenedifluoride porous layer/thin film polydimethylsiloxane dense layer composite membranes, membrane mass transfer coefficients are 2.55E−03, 2.82E−03 and 2.90E−03 m/s for TCE, TOL and DMS in N₂ at 30.0 ± 0.1 °C, respectively. For polyester/polyacrylonitrile porous layer/thin film polydimethylsiloxane dense layer composite membranes, they are higher, namely 4.28E−03, 4.55E−03 and 4.81E−03 m/s for TCE, TOL and DMS in N₂ at 30.0 ± 0.1 °C, respectively. Analysis of the contribution of the dense layer of both composite membranes to the total membrane resistance for mass transfer, showed that this contribution was small for both composite membranes. The higher mass transfer coefficients of the thin film polydimethylsiloxane composite membranes from this study in comparison to others from the literature are primarily due to improvement of the mass transfer characteristics of the porous layer. Analysis of the mass transfer characteristics of the different porous layers of which the total porous layer is composed, showed that the contribution of the porous “backing” layer for mechanical support can be substantial in comparison to the porous layer in contact with the dense layer.     

The effect of light on the viscosity and molecular mass of nitrocellulose

The photodegradation of a series of nitrocellulose (NC) samples with nitrogen contents ranging from 11.69% to 13.55% has been investigated by observing changes in molecular mass and viscosity using, respectively, size exclusion chromatography (SEC) and a modified cone and plate rheometer. When NC in γ-butyrolactone was subjected to UV light in the range 320-390 nm its specific viscosity (η_sp) was found to decrease noticeably, a change attributed to polymer chain scission and de-aggregation. This view was supported by an observed reduction in the mass average molecular mass (M_w). In contrast, irradiation with a single wavelength at 365 nm did not significantly change either η_sp or M_w and similar behaviour was observed when NC solutions were irradiated with visible light (400-500 nm). In the solid state, the photodegradation of water-wet NC is faster than that of the dried material, which is attributed to the catalytic effect of acids formed from the reaction between water and nitrogen oxides (NO_x) arising from NC decomposition. A higher degree of crystallinity in the NC, as found by X-ray diffraction (XRD), was shown to lead to a smaller decrease in viscosity and molecular mass. This is thought to be because the photodegradation reaction is suppressed in crystalline NC by more effective radical-radical recombination.     

Influence of the sample-solvent on protein retention,mass transfer and unfolding kinetics in hydrophobic interaction chromatography

Typical mobile phase employed in hydrophobic interaction chromatography contains cosmotropic salts, which promote retention and simultaneously reduce the protein solubility in the mobile phase. To increase mass overloading in the separation process the protein can be dissolved in a sample-solvent with concentration of salt lower than that in the mobile phase or in salt free solutions. However, this methodology may cause band splitting and band deformation, which results in yield losses. In this study, these phenomena were analyzed based on the retention behavior of two model proteins, i.e., lysozyme and bovine serum albumin. Retention of these proteins was accompanied by strong band broadening originated from slow rates of mass transfer and/or of adsorption–desorption process involving the protein conformational changes. The mass transport resistances and unfolding kinetics were found to contribute to the sample-solvent effects. To avoid band deformations the process variables such as the salt concentration and temperature were adjusted in such a way that complete resolution between band profile of the sample-solvent and the protein was achieved. For the process simulation a dynamic model, which accounted for underlying kinetics was used. General guidelines of the process design were developed.     

Shell-side mass transfer of hollow fibre modules in osmotic distillation process

The effect of packing density of hollow fibre modules on mass transfer in the shell side of osmotic distillation process was studied. The osmotic distillation experiments were carried out with several modules of the packing densities ranging from 30.6 to 61.2%. It was found that the Reynolds number was a function of packing density and packing density affected mass transfer performance. The shell-side mass transfer coefficient increased with the brine velocity. The membrane permeability can be predicted from the experimental flux at the maximum brine velocity. The mass transfer correlation was proposed in order to determine the shell-side mass transfer coefficient in the randomly packed modules for osmotic distillation process. The empirical correlation proposed was fitted to the experimental results and it was found that the mass transfer coefficients calculated from the proposed correlation were in good agreement with those from the experimental data. Comparison of the results obtained from the proposed correlation with other correlations in the literature was discussed.     

Photocatalytic degradation of ammonia and butyric acid in plug-flow reactor: Degradation kinetic modeling with contribution of mass transfer

Photocatalytic treatment of polluted air by odorous contaminants – ammonia and butyric acid – is investigated in a plug-flow reactor covered by non-woven fiber textile coated with TiO₂. For the first time, the single-component degradation pathway of ammonia by photocatalysis at ambient condition is highlighted. It appears fundamentally different compared to the butyric acid degradation pathway. The ammonia degradation pathway highlights a possible auto-accelerated behavior of the reaction. The chemical degradation kinetics follows the Langmuir–Hinshelwood model, though observed oxidation rates depend upon flow conditions in the reactor. Thus, interpretation of degradation results through a model considering the Langmuir–Hinshelwood approach and mass transfer phenomenon is presented. This model succeeds with a pair of determined kinetic constants and mass transfer coefficients to describe experimental results for different flow rates and for both pollutants, though they present wide dissimilarities in their degradation pathways.     

Experimental and theoretical study on propylene absorption by using PVDF hollow fiber membrane contactors with various membrane structures

Five kinds of asymmetric poly(vinylidene fluoride) (PVDF) hollow fiber membranes with considerable different porosities at the inner and outer surfaces of the membrane were prepared via thermally induced phase separation (TIPS) method and applied for propylene absorption as gas–liquid membrane contactors. A commercial microporous poly(tetrafluoroethylene) (PTFE) hollow fiber membrane was also used as a highly hydrophobic membrane. Experiments on the absorption of pure propylene into silver nitrate solutions were performed and the effects of membrane structure, inner diameter, silver nitrate concentration and absorbent liquid flow rate were investigated at 298 K. PVDF membranes prepared by using nitrogen as bore fluid had lower inner surface porosity than the membranes prepared with solvent as bore fluid. Except the membrane with a skin layer at the outer surface, propylene absorption flux was inversely proportional to the inner diameter of the hollow fiber membrane, and propylene absorption rate per fiber was almost the same. Propylene flux increased with increasing the silver nitrate concentration and also with increasing the absorbent flow rate.A mathematical model for pure propylene absorption in a membrane contactor, which assumes that the membrane resistance is negligibly small and the total membrane area is effective for gas absorption, was proposed to simulate propylene absorption rates. Experimental results were satisfactorily simulated by the model except for the membrane having a skin layer. The model also suggested that propylene is absorbed in silver nitrate solutions accompanied by the instantaneous reversible reaction. This paper may be the first experimental and theoretical study on propylene absorption in membrane contactors.     

Non-invasive monitoring of fouling in hollow fiber membrane via UTDR

Fouling is the most critical problem associated with membrane separations in liquid media. But it is difficult to control the inevitable membrane fouling because of its invisibility, especially on the inside surface of hollow fiber membranes. This study describes the extension of ultrasonic time-domain reflectometry (UTDR) for the real-time measurement of particle deposition in a single hollow fiber membrane. A transducer with a frequency of 10 MHz and polyethersulfone hollow fiber membranes with 0.8 mm inside diameter (ID) and 1.2 mm outside diameter (OD) were used in this study. The fouling experiments were carried out with 1.8 g/L kaolin suspension at flow rates 16.7 and 10.0 cm/s. The results show that UTDR technique is able to distinguish and recognize the acoustic response signals generated from the interfaces water/upper outside surface of the hollow fiber, lumen upside surface/water, water/lumen underside surface and lower outside surface/water in the single hollow fiber membrane module in pure water phase. The systemic changes of acoustic responses from the inside surfaces of the hollow fiber in the time- and amplitude-domain with operation time during the fouling experiments were detected by UTDR. It is associated with the deposition and formation of the kaolin layer on the inside surfaces. Further, the acoustic measurement indicates that the deposited fouling layer is denser on the lumen underside surface of the hollow fiber than that on the lumen upside surface as a result of weight. Moreover, it is found that the fouling layer grows faster on the inside surface of the hollow fiber at a flow rate of 10.0 cm/s than that at 16.7 cm/s due to the lower shear stress. The fouling layer formed is thicker at a flow rate of 10.0 cm/s than that at 16.7 cm/s. The flux decline data and SEM analysis corroborate the ultrasonic measurement. Overall, this study confirms that UTDR measurement will provide not only a new protocol for the observation of hollow fiber membrane fouling and cleaning, but also a quantitative approach to the optimization of the membrane bioreactor system.     

Experimental verification of pressure drop models in hollow fiber membrane

A new experimental method to obtain internal pressure profiles in a hollow fiber membrane was demonstrated. The experimentally obtained internal pressure profiles were compared with the theoretically calculated ones based on Hagen–Poiseuille equations. The experimental and theoretical results agreed very well in clean water conditions only when accurate membrane permeabilities and effective internal diameters were available. New experimental methods to obtain the two parameters were demonstrated. The same experimental technique was also applied for the submerged hollow fiber membranes filtering activated sludge to find out how internal pressure profiles were changing with time. Based on the pressure profiles, evidences that indicated the local flux near membrane exit was lower than those in adjacent area were found. This observation contradicted to the filtration models based on critical flux concept. It was considered that the cake layer collapse near the membrane exit was the cause. Though there was some degree of delay in pressures detection, the method demonstrated in this study provided a great accuracy when pressure profiles did not change rapidly.     

A numerical and experimental study of mass transfer in spacer-filled channels: Effects of spacer geometrical characteristics and Schmidt number

A systematic study is presented on the effect of both Reynolds (Re) and Schmidt (Sc) numbers on Sherwood (Sh) number, for narrow channels with spacers, closely simulating conditions of feed-side channels in spiral-wound modules. Results of direct numerical simulations performed for the three-dimensional geometries resulting from non-woven cylindrical filament (net-type) spacers show the significant influence of spacer geometry on local Sh distributions. These distributions exhibit a tendency to be displaced towards lower values for more sparse spacer geometries, and towards higher values as the angle between crossing filaments is increased. Additionally, the distribution of the local time-averaged mass transfer coefficients is generally similar to the corresponding distribution of shear stresses at the channel walls, with a tendency to exhibit closer similarity with increasing Sc, as one would expect. To validate the results of numerical simulation, a significant amount of mass transfer data is reported for nine different prototype spacer geometries, plus a common commercial spacer, and three Sc numbers in each case. Correlations of average Sh are obtained for each geometry, in terms of Re and Sc numbers; the exponent of Sh dependence on Sc is near 0.4, as is also obtained from the numerical simulations. Moreover, in agreement with the numerical results, the experimental data reveal a similar trend in the dependence of the average Sh number on spacer geometrical characteristics, namely decreasing with increasing ratio L/D (of cell side L over filament diameter D) and increasing with the filaments crossing angle β. A mass transfer correlation is also proposed for the square-cell commercial spacer commonly used in RO/NF modules.     

Electrochemical pressure impedance spectroscopy for investigation of mass transfer in polymer electrolyte membrane fuel cells

Mass transfer phenomena in membrane fuel cells are complex and diversified because of the presence of complex transport pathways including porous media of very different pore sizes and possible formation of liquid water. Electrochemical impedance spectroscopy, although allowing valuable information on ohmic phenomena, charge transfer and mass transfer phenomena, may nevertheless appear insufficient below 1 Hz. Use of another variable, that is, back pressure, as an excitation variable for electrochemical pressure impedance spectroscopy is shown here a promising tool for investigations and diagnosis of fuel cells.     

Predicting the effect of membrane spacers on mass transfer

Like many separation processes, ultrafiltration and reverse osmosis are often compromised by concentration polarization. Such polarization can be mitigated by static mixers and other flow barriers placed as spacers next to the membrane surface. These spacers can be shaped like ladders, herringbones, and helices. The effect of these spacers can be successfully predicted without adjustable parameters from extensions of the Lévêque equation. The predictions are in agreement with results of computational fluid mechanics and with electrochemical experiments. They supply a tool for optimizing spacer design.     

Viscoelasticity and mass transfer in phenol–CTAB aqueous systems

The rheological and mass transport properties of phenol in micellar solutions of hexadecyltrimethylammonium bromide (CTAB) were studied by rheometry and spectrophotometry. The presence of phenol located between headgroups of the CTAB diminishes the repulsive forces between the cationic groups and induces a sharp increase in viscosity that is attributed to the one-dimensional micellar growth favoring the formation of worm-like micelles. It is found that the mass transfer of phenol between two immiscible phases is significantly retarded by the presence of CTAB. The transfer is particularly slow when the diffusion takes place from a surfactant solution phase to an organic phase. This behavior is attributed to the phenol–surfactant interaction that leads to micellar growth and viscoelastic behavior. However, at elevated temperature, viscosity decreases and mass transfer increases. This particular rheological behavior offers the possibility of regulating the mass transfer, which might be interesting for applications.     

固体粒子对板式膜吸收过程的传质强化

分别采用纯CO2-去离子水和不同浓度的NaOH溶液为实验体系,在板式膜器中研究了第三相固体粒子对膜吸收过程传质效果的影响．分别考察了在不同粒子种类、搅拌转速、传质体系、化学反应强度、膜孔隙率等因素下固体粒子对传质强化的影响．结果表明,随着粒子固含率的增大,传质系数和增强因子均有所提高,当粒子固含率增大到一定范围后,传质系数和增强因子的变化趋于平缓．在固含率一定的条件下,不同种类的固体粒子对膜吸收过程的强化效果随着固体粒子密度的增加而减小．传质系数随着搅拌转速的增大而增大,但高搅拌转速下固体粒子的强化作用减弱．膜吸收过程的传质系数和增强因子随着化学反应强度的增强而增加．随着粒子固含率的增大,不同膜孔隙率对传质效果的差异减小,且孔隙率越小,固体粒子对膜吸收传质过程的强化效果越好．其中,对于纯CO2-去离子水体系,当孔隙率为20％,粒子固含率为1．5gL^（-1）时,固体粒子的加入可使传质系数提高1．45倍,增强因子可达2．45．     

On the structure of the single-phase flow field in hollow fiber membrane modules during filtration

Whereas the structure of the flow field generated in the hollow fiber membrane modules operating as liquid–liquid or gas–liquid contactors has been studied extensively theoretically, this is not the case for the much more complex flow field generated during the filtration operation of the same type of modules. The present work is a first approach to analyze and understand the particular flow field. The mathematical problem is formulated and then geometrical and physical simplifications are introduced in order to decompose the full problem in a series of simpler sub-problems. In addition to the presentation of the general structure and the features of the problem, the focus of the present work is to derive all possible analytical solutions of the sub-problems. Several results based on analytical or simple numerical approaches are also presented.     

Heat and moisture transfer in application scale parallel-plates enthalpy exchangers with novel membrane materials

Parallel-plates enthalpy exchangers are one of the most commonly encountered energy recovery devices that are used to simultaneously transfer both sensible heat and moisture between fresh air and exhaust ventilation air. For such equipments, the water vapor sorption properties of the plate materials have tremendous impacts on system performance. In this investigation, three different materials, namely, common paper, CA (cellulose acetate) membrane and a modified CA membrane) are selected as the plate materials for three enthalpy exchangers. Sorption curves and contact angles of these three materials are measured to reflect their hydrophilicity. The steady-state sensible and latent effectiveness of the three exchangers are tested in a special test rig, and the test results are compared with the model predictions. A heat and moisture transfer model for the enthalpy exchangers is proposed. The effects of the varying operating conditions like air flow rates, temperature, and humidity on the sensible and latent effectiveness are evaluated. Both the numerical and experimental results indicate that the moisture resistance through plates is co-determined by thickness, sorption slope, and sorption potential. Moisture diffusivity in various materials is in the same order. So when the plate thickness is fixed, the higher the sorption slopes are, the higher the latent performance is. Of the three exchangers, the exchanger with the modified CA membrane material has the highest performance due to small thickness, steep sorption slope, and large sorption potentials. The paper exchanger has a latent effectiveness of 0.4, while the membranes have latent effectiveness of greater than 0.7.     

Sequential Electrochemical Polymerization of Aniline and Their Derivatives Showing Electrochemical Activity at Neutral pH

Sequential electropolymerization of aniline followed by an aniline derivative bearing an ion moiety is presented. The studied derivatives contain sulfonic, carboxylate or amino groups. Its electrochemical behavior at acid and neutral pH is studied by cyclic voltammetry combined with quartz crystal microbalance or probe beam deflection in order to assess the mass transfer process involved in these new modified electrodes. All of them show a stable and quasi‐reversible electrochemical behavior at neutral pH that can be attributed to a self‐doping process. These new modified electrodes can be further modified due to the presence of functional groups.     

Quantification of oxygenated volatile organic compounds in seawater by membrane inlet-proton transfer reaction/mass spectrometry

The role of the ocean in the cycling of oxygenated volatile organic compounds (OVOCs) remains largely unanswered due to a paucity of datasets. We describe the method development of a membrane inlet-proton transfer reaction/mass spectrometer (MI-PTR/MS) as an efficient method of analysing methanol, acetaldehyde and acetone in seawater. Validation of the technique with water standards shows that the optimised responses are linear and reproducible. Limits of detection are 27 nM for methanol, 0.7 nM for acetaldehyde and 0.3 nM for acetone. Acetone and acetaldehyde concentrations generated by MI-PTR/MS are compared to a second, independent method based on purge and trap-gas chromatography/flame ionisation detection (P&T-GC/FID) and show excellent agreement. Chromatographic separation of isomeric species acetone and propanal permits correction to mass 59 signal generated by the PTR/MS and overcomes a known uncertainty in reporting acetone concentrations via mass spectrometry. A third bioassay technique using radiolabelled acetone further supported the result generated by this method. We present the development and optimisation of the MI-PTR/MS technique as a reliable and convenient tool for analysing seawater samples for these trace gases. We compare this method with other analytical techniques and discuss its potential use in improving the current understanding of the cycling of oceanic OVOCs.