Implications of inhomogeneous distribution of concentration polarization for interpretation of pressure-driven

A number of CFD studies have demonstrated that there is a considerable inhomogeneity of extent of Concentration Polarization (CP) over the membrane surface especially in spacer-filled feed channels. However, the consequences of this inhomogeneity for the interpretation of measurements of solute rejection in pressure-driven membrane processes have received little attention. This study uses a simple model of locally-1D CP combined with a postulated probability distribution of unstirred-layer thickness over the membrane thickness. In this way, we obtain transparent analytical results and can consider qualitative consequences of inhomogeneous distribution of CP over membrane surface. Our analysis shows that disregarding the CP distribution under-estimates the CP of strongly positively-rejected solutes and over-estimates the CP for the negatively-rejected ones. This observation is especially important for the interpretation of ion rejection from multi-ion solutions in nanofiltration where strong positive and pronounced negative rejections can occur simultaneously for solutes of different charges. We conclude that for reliable interpretation of pressure-driven membrane measurements it is desirable to reduce the inhomogeneity of CP distribution to a minimum in membrane-testing devicesPeer ReviewedPostprint (author's final draft

Characterization and modelling of micro and nanofluidic systems

Lab-on-a-chip arrangements are ever more frequently used for the miniaturization of chemical and biochemical analysis. In these arrangements, all the manipulations of analyte transport, separation, mixing with reactants and detection are integrated and implemented at the scale of a microchip of several cm in size. This makes possible a dramatic reduction in the required amounts of analytes and reactants, as well as in the time of analysis. Besides that, automation and high-throughput operations (due to parallelization) become much easier than in the conventional "macro-laboratory" environments. According to the great interest in the development of new porous materials including their subsequent integration into biomedical devices and industrial applications, the description of the characteristics of nanoporous media (for example membranes) and the development of characterization techniques are crucial for controlling the behavior of systems that include separation and purification processes with such technologies. Within this thesis various developments in the field of microfluidics, separation and purification of substances has been carried out: For the field of microfluidics, this study may be useful for the description of the first stages of the concentration polarization in microfluidic systems coupling membrane technology or micro/nano interfaces. Furthermore, it was shown that for such systems, Taylor-Aris theory is applicable locally in large open microchannels within a range of Peclet numbers. Furthermore, it was possible to derive a simple analytical approach for internal concentration gradient within long channels in terms of only a few parameters, determined numerically. This approach is useful for developing future experimental studies. In equipment used for measuring the zeta potential of porous media, the variation in the channel height is technically possible. This thesis shows that under such conditions, the fluid flow can become undeveloped turbulent, which provokes that conventional approaches to the interpretation of electrokinetic measurements should be changed accordingly. A mathematical model for arbitrary electrolytes mixtures has been defined to describe the transport phenomena occurring in several osmotic separation processes. The limited number of adjustable parameters contained in this model makes possible its unequivocal determination from a limited set of experimental data. According to the results of this work, hollow fibers membrane contactors are useful as a polishing step for removing low levels of ammonia in water. It has been determined and validated experimentally a mathematical model which helps to describe the influence of operating conditions, such as flow, ammonia concentration and pH of the system for both configurations, closed and open loop. These results are important for designing production systems of ultrapure water that can be used in the production of hydrogen by water electrolysis. The application of microfluidics technologies at industrial scale is one of the main challenges faced on this knowledge field; however, there are some devices that are already being used systematically at industrial level for separation purposes that fulfil the criteria for being considered within that group of technologies. This thesis establishes patterns and basic concepts that can serve as basis for the characterization and description of miniature versions of well-known separation processes, which in turn, can be used for the development of processes in new biochemical applications.La miniaturización de los análisis químicos y bioquímicos está cada vez utiliza más utilizada. Todas las manipulaciones de transporte de las muestras, la separación, la mezcla con los reactivos y la detección se integren y apliquen a escala de un microchip de varios centímetros de tamaño. Esto hace posible una reducción dramática en las cantidades requeridas de muestra y reactivos, así como en el tiempo del análisis. Además de eso, las operaciones de automatización y de alto rendimiento se vuelven mucho más fáciles que en los entornos convencionales "macro-laboratorio". De acuerdo con el gran interés en el desarrollo de nuevos materiales porosos incluyendo su posterior integración en dispositivos biomédicos y aplicaciones industriales, la descripción de las particularidades de los medios nanoporosos (por ejemplo membranas) y el desarrollo de técnicas de caracterización son cruciales para controlar el comportamiento de los sistemas que incluyen procesos de separación y purificación con dichas tecnologías. En esta tesis se han llevado a cabo diferentes avances en el campo de la microfluídica, la separación y purificación de sustancias: Para el campo de la microfluídica, este estudio puede ser útil para la descripción de las primeras etapas de la polarización en los sistemas microfluídicos que acoplan tecnología de membranas o micro/nano interfaces. Por otro lado, se demostró que para tales sistemas, la teoría de Taylor-Aris es aplicable localmente dentro de microcanales abiertos en una amplia gama de números de Péclet. Además, fue posible derivar una aproximación analítica sencilla para el gradiente de concentración interno dentro de canales largos en términos de sólo unos pocos parámetros, determinados numéricamente. Esta aproximación es útil para desarrollar futuros estudios experimentales. En algunos equipos usados para la medición del potencial zeta de medios porosos, la variación de la altura del canal es técnicamente posible. En esta tesis se muestra que en estas condiciones, el flujo de fluido puede llegar a ser de transición a turbulento y los enfoques convencionales para la interpretación de las mediciones electrocinéticas debe modificarse en consecuencia. Se definió un modelo matemático que permite describir de manera sencilla, fenómenos de transporte que ocurren en diversos procesos de separación osmóticos, para mezclas de electrolitos arbitrarias. El número limitado de parámetros ajustables que contiene este modelo hace factible su determinación inequívoca a partir de un conjunto limitado de datos experimentales. De acuerdo con los resultados de esta tesis, los contactores de membrana con fibras huecas son útiles como etapa de pulido para la eliminación de bajos niveles de amonio en agua. Se ha determinado y validado experimentalmente un modelo matemático el cual ha ayudado a describir la influencia de las condiciones de funcionamiento, tales como flujo, concentraciones de amonio y pH del sistema para ambas configuraciones, de lazo cerrado y abierto. Dichos resultados son útiles para el diseño de sistemas de producción de agua ultra pura que puede ser usada en la producción de hidrogeno por electrolisis. La aplicación de las tecnologías de microfluidos a escala industrial es uno de los principales retos que enfrentar en este campo del conocimiento; sin embargo, existen algunos dispositivos que ya se están utilizando de forma sistemática a nivel industrial para fines de separación que cumplen criterios necesarios para considerarlos dentro del grupo de las tecnologías de microfluídica. Acotando a los resultados presentados en microfluídica, con este trabajo se han establecido patrones y definido conceptos básicos, dentro de este campo de la ciencia, que pueden servir como bases en la caracterización y la descripción de versiones en miniatura de procesos de separación bien conocidos, los cuales se pueden usar para el desarrollo de procesos en nuevas aplicaciones bioquímicas

Hydrodynamic dispersion in long microchannels under conditions of electroosmotic circulation: II. Electrolytes

This work describes the steady-state transport of an electrolyte due to a stationary concentration difference in straight long channels under conditions of electroosmotic circulation. The electroosmotic flow is induced due to the slip produced at the charged channel walls. This flow is assumed to be compensated by a pressure-driven counterflow so that the net volume flow through the channel is exactly zero. Owing to the concentration dependence of electroosmotic slip, there is an involved coupling between the solute transfer, hydrodynamic flow and charge conservation. Nevertheless, for such a system the Taylor–Aris dispersion (TAD) theory is shown to be approximately applicable locally within an inner part of the channel for a wide range of Péclet numbers (Pe) irrespective of the concentration difference. Numerical simulations reveal only small deviations from analytical solutions for the inner part of the channel. The breakdown of TAD theory occurs within boundary regions near the channel ends and is related to the variation of the dispersion mechanism from the purely molecular diffusion at the channel ends to the hydrodynamic dispersion within the inner part of the channel. This boundary region is larger at the lower-concentration channel edge and its size increases nearly linearly with Pe number. It is possible to derive a simple analytical approximation for the inner profile of cross-section-averaged electrolyte concentration in terms of only few parameters, determined numerically. Such analytical approximations can be useful for experimental studies of concentration polarization phenomena in long microchannels.Peer ReviewedPostprint (author's final draft

Valorization of ammonia concentrates from treated urban wastewater using liquid–liquid membrane contactors

The removal of ammonium from tertiary effluents by zeolites generates basic ammonia concentrates (up to 1–3 gNH3/L in 1–2 g NaOH/L). This study evaluates the use of hollow fibre liquid–liquid membrane contactors (HFMCs) as a concentration and purification step for ammonia effluents to produce NH4NO3 and (NH4)2(HPO4) solutions for potential use as liquid fertilizers. The influence of various operational parameters (i.e., flow rate, initial ammonia concentration and stripping acid concentration) was investigated using a closed-loop setup. Due to the high basicity of the ammonia feed streams (pH > 12), the mass transport process was primarily controlled by the free acid concentration in the stripping phase (e.g., HNO3 and H3PO4). A mass transport algorithm to predict the pH of the stripping stream was developed to describe the contactor performance, predict the requirements of the free acid concentration in the stripping phase and optimize the ammonia recovery. Therefore, the closed-loop configuration allowed for ammonia recovery ratios higher than 98% when the required free acid concentration of the stripping phase was maintained. The exhausted NH3/NaOH streams after NH3 removal can be re-used for regeneration of the ammonium-exhausted zeolite filters.Postprint (author's final draft

Asymmetric electroosmotic pumping across porous media sandwiched with perforated ion-exchange membranes

To have non-zero net flow in AC electroosmotic pumps, the electroosmosis (EO) has to be non-linear and asymmetric. This can be achieved due to ionic concentration polarization. This is known to occur close to micro-/nano-interfaces provided that the sizes of the nanopores are not too large compared to the Debye screening length. However, operation of the corresponding EO pumps can be quite sensitive to the solution concentration and, thus, unstable in practical applications. Concentration polarization of ion-exchange membranes is much more robust. However, the hydraulic permeability of the membrane is very low, which makes EO flows through them extremely small. This communication shows theoretically how this problem can be resolved via making scarce microscopic perforations in an ion-exchange membrane and putting it in series with an EO-active nano-porous medium. The problem of coupled flow, concentration and electrostatic-potential distributions is solved numerically by using finite-element methods. This analysis reveals that even quite scarce perforations of micron-scale diameters are sufficient to observe practically-interesting EO flows in the system. If the average distance between the perforations is smaller than the thickness of the EO-active layer, there is an effective homogenization of the electrolyte concentration and hydrostatic pressure in the lateral direction at some distance from the interface. The simulations show this distance to be somewhat lower than the half-distance between the perforations. On the other hand, when the surface fraction of perforations is sufficiently small (below a fraction of a percent) this “homogeneous” concentration is considerably reduced (or increased, depending on the current direction), which makes the EO strongly non-linear and asymmetric. This analysis provides initial guidance for the design of high-productivity and inexpensive AC electroosmotic pumps.Peer ReviewedPostprint (published version

Simultaneous ammonium and phosphate recovery and stabilization from urban sewage sludge anaerobic digestates using reactive sorbents

The use of low-cost inorganic sorbents as a new sustainable strategy to enhance the valorization of nutrients (N-P-K), from the urban water cycle (e.g., side streams from sewage sludge anaerobic digestion), in agriculture applications is presented. The simultaneous recovery and stabilization of ammonium and phosphate by using a mixture of two reactive sorbents (Na and K zeolites and magnesium oxide) was evaluated. The nutrients stabilization process, favoured at alkaline pH values, is carried out by a) the precipitation of phosphate ions with magnesium and/or ammonium ions and b) the sorption of ammonium by Na- and K-zeolites. MgO(s) promoted the stabilization of phosphate as bobierrite (Mg3(PO4)2(s)) or struvite (MgNH4PO4(s)) depending on the applied dose. Doses with the stoichiometric molar ratio of Mg/P promote the formation of bobierrite, while molar ratios higher than 3 favour the formation of struvite. Na zeolites (NaP1-NA, NaP1-IQE) demonstrated efficiency on ammonium stabilization between 60 ± 2 (for 15 gZ/L) to 90 ± 3% (for 50 gZ/L). The ammonium recovery efficiency is limited by the zeolite sorption capacity. If the target of the fertilizing criteria should include K, then the use of a K-zeolite (e.g., 5AH-IQE) provides a good solution. The optimum pH for the precipitation of struvite and bobierrite is 9.5 and the optimum pH for ammonium removal is between 4 and 8.5. N is present in higher concentrations (up 0.7–1 g NH4+/L) when pH is ranged between 8.2 and 8.6. The ammonium recovery ratios were better than those previously reported using only magnesium oxide or even a more expensive reagent as newberrite (MgHPO4(s)). The recovery mechanisms described generate low-solubility stabilized nutrients forms that potentially can be applied as slow-release fertilizers in agriculture. Thus, the use in agriculture of blends of digested sludge with low-solubility stabilized nutrients forms will improve soils quality properties in terms of organic matter and nutrients availability.Peer ReviewedPostprint (author's final draft

Simultaneous ammonium and phosphate recovery and stabilization from urban sewage sludge anaerobic digestates using reactive sorbents

The use of low-cost inorganic sorbents as a new sustainable strategy to enhance the valorization of nutrients (N-P-K), from the urban water cycle (e.g., side streams from sewage sludge anaerobic digestion), in agriculture applications is presented. The simultaneous recovery and stabilization of ammonium and phosphate by using a mixture of two reactive sorbents (Na and K zeolites and magnesium oxide) was evaluated. The nutrients stabilization process, favoured at alkaline pH values, is carried out by a) the precipitation of phosphate ions with magnesium and/or ammonium ions and b) the sorption of ammonium by Na- and K-zeolites. MgO(s) promoted the stabilization of phosphate as bobierrite (Mg3(PO4)2(s)) or struvite (MgNH4PO4(s)) depending on the applied dose. Doses with the stoichiometric molar ratio of Mg/P promote the formation of bobierrite, while molar ratios higher than 3 favour the formation of struvite. Na zeolites (NaP1-NA, NaP1-IQE) demonstrated efficiency on ammonium stabilization between 60±2 (for 15gZ/L) to 90±3% (for 50gZ/L). The ammonium recovery efficiency is limited by the zeolite sorption capacity. If the target of the fertilizing criteria should include K, then the use of a K-zeolite (e.g., 5AH-IQE) provides a good solution. The optimum pH for the precipitation of struvite and bobierrite is 9.5 and the optimum pH for ammonium removal is between 4 and 8.5. N is present in higher concentrations (up 0.7-1gNH4+/L) when pH is ranged between 8.2 and 8.6. The ammonium recovery ratios were better than those previously reported using only magnesium oxide or even a more expensive reagent as newberrite (MgHPO4(s)). The recovery mechanisms described generate low-solubility stabilized nutrients forms that potentially can be applied as slow-release fertilizers in agriculture. Thus, the use in agriculture of blends of digested sludge with low-solubility stabilized nutrients forms will improve soils quality properties in terms of organic matter and nutrients availability

Ammonium removal by liquid–liquid membrane contactors in water purification process for hydrogen production

© 2014 Balaban Desalination Publications. All rights reserved. In this work, a liquid–liquid membrane contactor (LLMC) was evaluated to remove ammonia traces from water used for hydrogen production by electrolysis. Three operational parameters were evaluated: the feed flow rate, the initial ammonia concentration in the water stream, and the pH of solution. Synthetic aqueous solutions with ammonium concentration of 5–25 mg L-1 and a sulfuric acid solution (pH 2) were supplied to the LLMC in countercurrent and open-loop configuration with flow rates between 2.72 × 10-6 and 22.6 × 10-6 m3 s-1 and the pH values of the solution with ammonium between 8 and 11. A 2D numerical model was developed considering advection–diffusion equation inside a single fiber of the lumen with fully developed laminar flow and liquid–gas equilibrium in the membrane–solution interface. Predictions of the model were then validated against experimental data, which were found to be in good agreement. According to both, experimental data and numerical predictions, the hollow-fiber membrane contactor technology is a suitable alternative to remove ammonium from water and to feed the membrane distillation unit in order to fulfill water quality requirements for electrolysis-based hydrogen production.Peer ReviewedPostprint (author's final draft

3D Electrophoresis-assisted lithography (3DEAL): 3D molecular printing to create functional patterns and anisotropic hydrogels

The ability to easily generate anisotropic hydrogel environments made from functional molecules with microscale resolution is an exciting possibility for the biomaterials community. This study reports a novel 3D electrophoresis‐assisted lithography (3DEAL) platform that combines elements from proteomics, biotechnology, and microfabrication to print well‐defined 3D molecular patterns within hydrogels. The potential of the 3DEAL platform is assessed by patterning immunoglobulin G, fibronectin, and elastin within nine widely used hydrogels and characterizing pattern depth, resolution, and aspect ratio. Furthermore, the technique's versatility is demonstrated by fabricating complex patterns including parallel and perpendicular columns, curved lines, gradients of molecular composition, and patterns of multiple proteins ranging from tens of micrometers to centimeters in size and depth. The functionality of the printed molecules is assessed by culturing NIH‐3T3 cells on a fibronectin‐patterned polyacrylamide‐collagen hydrogel and selectively supporting cell growth. 3DEAL is a simple, accessible, and versatile hydrogel‐patterning platform based on controlled molecular printing that may enable the development of tunable, chemically anisotropic, and hierarchical 3D environments

Model of forward osmosis through composite/asymmetric membranes : effects of support inhomogeneity and solution non-ideality

The processes of Forward Osmosis and Pressure-Retarded Osmosis are strongly influenced by Internal Concentration Polarization occurring within their porous supports. Models of this important phenomenon usually assume that the support layer can be described by using a single space-independent value of effective diffusion coefficient of solute (or S-parameter). At the same time, FO/PRO supports are known to be not macroscopically homogeneous. Via a simple transformation of a modified convection-diffusion equation we show that the simple model with a constant effective diffusion coefficient is applicable to macroscopically inhomogeneous supports provided that this coefficient is understood as the harmonic average of the space-dependent one. Using the arithmetic average porosity leads to an overestimation of draw solute diffusivity within the support layer. The effects of draw solute non-ideality were explicitly and rigorously accounted for. We also demonstrate theoretically that the same harmonic average diffusive hindrance factor can be estimated from direct measurements of diffusion across the membrane supports if those are separately available. The effects of non-ideality are strongly dependent on draw solute choice. It is shown that, in the case of NaCl and KCl, draw solute non-ideality has fairly limited implications for FO and PRO flux prediction. In the case of MgSO4, non-ideality significantly influences expected fluxes: ignoring non-ideality leads to an overestimation of fluxes by a factor of two. In the case of MgCl2, despite strong solute non-ideality, the error is relatively limited, due to an increase of the osmotic coefficient offsetting a decrease of diffusivity as a function of MgCl2 concentration