Forward osmosis (FO) is an osmotically driven process that uses a high concentration draw solution to pull water across a semipermeable membrane from a feed solution. Wastewater, seawater, or other contaminated water sources may be used as a feed solution. In FO, the final product is not clean water but a diluted draw solution. However, FO may be combined with another process, e.g. reverse osmosis (RO). The resulting hybrid process offers advantages compared to the RO process in, for example, seawater desalination. Thin-film composite (TFC) membranes have been used in pressurized processes such as RO due to their thick porous support layer and their ability to endure high hydrostatic pressures. However, the presence of a thick porous layer is detrimental for FO processes. It is responsible for the internal concentration polarization (ICP) inside the membrane, reducing the osmotic driving force and the overall water flux. The characterization of membranes in FO applications is key for understanding how different intrinsic parameters affect membrane performance. In this work, a previously developed methodology for characterizing TFC membranes was improved. Experimental data was obtained from a laboratory-scale FO system, and the experimental data was used to determine three intrinsic transport parameters, namely the water permeance, the salt permeance and the porous layer structural parameter. With this method, the characterization of TFC membranes can be achieved based exclusively on FO data. A sensitivity analysis has highlighted the impact of the intrinsic transport parameters on an FO membrane performance.

Membrane gas separation became an industrial reality in the late 1970s with Monsanto's first commercial asymmetric hollow fiber membrane modules. Innovations in membrane separations result from new materials that exhibit an improved permeability and are more selective than their predecessors, with materials commonly compared to the "upper bound line." Accurate determination of the three transport properties which characterize a membrane, permeability (P), diffusivity (D), and solubility (S), is thus of great interest to exceed the current upper bound line. Also, proper characterization of membrane materials enables enhancing current commercial membrane processes or allows for new applications. All three transport properties, P, S, and D, can be determined using a single dynamic gas permeation experiment in a constant volume (CV) system, commonly called the time-lag method. This work presents the next-generation CV system that utilizes the two-tank volume concept, namely a reference volume and a working volume. Compared to the previous iteration, the pressure in the reference volume can be reduced to the anticipated pressure in the working volume after initiating the gas permeation experiment. This allows monitoring of the pressure decay in the working volume (i.e., gas permeation into the membranes) using a high-resolution differential pressure transducer (DPT) right after initiating the experiment. The new system's operation is demonstrated by simultaneous monitoring of the upstream pressure decay and the downstream pressure rise during the time-lag experiments using a polyphenylene oxide (PPO) membrane. The values determined using the pressure decay method are compared to those determined using the downstream method to identify any limitations still present in the current iteration of the CV system. To set a reliable benchmark value to compare against, the downstream receiver was redesigned, and an optimal configuration was identified, which was associated with negligible resistance to gas accumulation and, thus, a minor error in the experimental time lag downstream from the membrane. Furthermore, a temperature enclosure was built to minimize errors caused by the constant temperature assumption during the time lag analysis. Additionally, the temperature-controlled enclosure allows for transport properties temperature dependence to be quantified by determining the activation energy of permeability, diffusion, and the enthalpy of solution for a given gas/polymer system.

In this study, membranes were made from three polyvinylidene fluoride (PVDF) polymers individually and the blend systems of high (H) and low (L) molecular weight PVDF by phase inversion process. After investigating membrane casting solutions’ viscous and thermodynamic properties, the membranes so fabricated were characterized by scanning electron microscopy, gas permeation tests, porosity measurement, contact angle (CA) and liquid entry pressure of water (LEPw) measurement, and further subjected to vacuum membrane distillation (VMD) in a scenario that was applicable for cooling processes, where the feed water temperature was maintained at 27℃. It was found that PVDF solutions’ viscosities and thermodynamic instabilities were determined by the types of PVDF employed in single polymer systems and the mixing ratios of two PVDF polymers in blend systems. Thus the membrane properties and performances were influenced by the aforesaid factors as well. In single polymer systems, it was found that the membrane surface roughness and porosity increased with an increase in molecular weight. Among all the membranes casted in this study, the water vapor flux of VMD was found to be the highest at the intermediate range of H:L ratio, i.e., 4:6, at which the thickness of the sponge-like layer showed a minimum, the finger-like macro-voids formed a more orderly single-layer structure, and the LEPw showed a minimum. A conclusion can be made that blend systems of high molecular weight PVDF polymers and low molecular weight PVDF polymers could be used to optimize membrane performance in vacuum membrane distillation.

Acid Doped Polybenzimidazole Membranes for High Temperature Proton Exchange Membrane Fuel Cells Author: Ahmet &Ouml / zg&uuml / r Yurdakul One of the most popular candidates for high temperature PEMFC&rsquo / s is phosphoric acid doped polybenzimidazole (PBI) membrane due to its thermal and mechanical stability. In this study, high molecular weight PBI was synthesized by using PPA polymerization. The stirring rate of reaction solution was optimized to obtain high molecular weight. The inherent viscosity of polymer was measured at four points in 96 percent sulphuric acid solution at 30 degree centigrade by using an Ubbelohde viscometer. The highest average molecular weight was found as approximately 120,000 using the Mark-Houwink equation. The polymer was dissolved in N,N-dimethylacetamide at 70 degree centigrade with an ultrasonic stirrer. The membranes cast from this solution were doped with phosphoric acid solutions at different concentrations. The doping levels of the membranes were 6, 8, 10 and 11 moles phosphoric acid/PBI repeat unit. The mechanical strength of the acid doped membranes measured by tensile tests were found as 23, 16, 12 and 11 MPa, respectively. Conductivity measurements were made using the four probe technique. The membranes were placed in a conductivity cell and measurements were taken in humidity chamber with temperature and pressure control. The conductivity of membranes was measured at 110, 130 and 150 degree centigrade in both dry air and water vapor. The highest conductivity was 0.12 S/cm at 150 degree centigrade and 33 percent relative humidity for the membrane doped with 11 moles of H3PO4. The measurements showed that conductivity increased with increasing doping and humidity. Moreover, membranes had acceptable conductivity levels in dry air.

In this study, membranes were made from three polyvinylidene fluoride (PVDF) polymers individually and the blend systems of high (H) and low (L) molecular weight PVDF by phase inversion process. After investigating membrane casting solutions’ viscous and thermodynamic properties, the membranes so fabricated were characterized by scanning electron microscopy, gas permeation tests, porosity measurement, contact angle (CA) and liquid entry pressure of water (LEPw) measurement, and further subjected to vacuum membrane distillation (VMD) in a scenario that was applicable for cooling processes, where the feed water temperature was maintained at 27℃. It was found that PVDF solutions’ viscosities and thermodynamic instabilities were determined by the types of PVDF employed in single polymer systems and the mixing ratios of two PVDF polymers in blend systems. Thus the membrane properties and performances were influenced by the aforesaid factors as well. In single polymer systems, it was found that the membrane surface roughness and porosity increased with an increase in molecular weight. Among all the membranes casted in this study, the water vapor flux of VMD was found to be the highest at the intermediate range of H:L ratio, i.e., 4:6, at which the thickness of the sponge-like layer showed a minimum, the finger-like macro-voids formed a more orderly single-layer structure, and the LEPw showed a minimum. A conclusion can be made that blend systems of high molecular weight PVDF polymers and low molecular weight PVDF polymers could be used to optimize membrane performance in vacuum membrane distillation.

Several commercially available reverse osmosis (RO) membranes were characterized with aqueous solutions of ammonium sulfate, potassium triphosphate, and mixtures of these two salts at different feed concentrations, compositions and pressures. The objective of this study was to investigate the rejection of these solutes, in particular the ammonium ion (NH4+), by different RO membranes. The aqueous solutions were assumed to come from an anaerobic digester via a process, currently under investigation by CHFour Biogas Inc., to maintain low concentrations of ammonia in the digester in order to maximize the biogas production. The ammonium ions present in the liquid produced from the process are then concentrated using membrane separation. The concentrated ammonium solution would be a valuable fertilizer that could be used by agriculture. The membranes were characterized with three models: the solution-diffusion model, the Kedem-Katchalsky model, also known as the irreversible thermodynamics model, and the Donnan Steric Pore Model (DSPM). The solution-diffusion and irreversible thermodynamics models were found to be inadequate for proper membrane characterization and the use of the DSPM model yielded membrane properties in good agreement with those found in already existing literature. The pore radius of investigated membranes ranged from 0.39 to 0.51 nm. The effect of pH on membrane surface charge was also studied, with the conclusion that increases in pH led to increasingly negative surface charges. This affected the transport of individual ions through the membrane due to preferential passage of the counter-ions. The effects of applied pressure on the stoichiometric nature of salt rejections were also studied. The minimal observed rejection from the range of experiments carried out using ammonium sulfate was 93%Non-stoichiometric rejections of ions were also observed in the experiments with single and multiple solutes. Furthermore, the rejection of ammonium ions in the presence of other ions (K+, SO42-, PO43-) increased as feed concentration increased, which was a result of the synergistic effects of feed pH and ionic interactions. The minimum NH4+ rejection in the presence of other ions was 95.4%, which suitability using RO membranes for concentration of ammonium from dilute aqueous solutions.

Cette étude a été consacrée à la purification et au fractionnement de mélanges de cyclodextrines par procédés membranaires (NF, UF). Les cyclodextrines (CD) sont des oligosaccharides cycliques constituées de 6 à plus de 60 unités de glucose (CD6-CD60). Elles sont synthèsées en mélange à partir de la bioconversion de l'amidon. Dans un premier temps, la complexation ultrafiltration a été appliquée pour séparer la CD6 et la CD7. Au cours de cette étude, différents paramètres comme la pression, le rapport stœchiométrique entre CD et agent complexant et le rapport massique entre CD ont été étudiés. Il s'est avéré que ces facteurs pouvaient agir sur la sélectivité de séparation. La diafiltration avec un facteur de réduction volumique de 3 a été utilisée, en présence d'Igepal (agent complexant), pour séparer la CD6 et la CD7. Les résultats obtenus sont assez intéressants vu qu'après 4 diafiltrations la CD6 a été récupérée dans le perméat avec une pureté et un rendement respectivement égal à 86 et 71%.Dans une deuxième partie, nous nous sommes intéressés au fractionnement d'un mélange brut de cyclodextrines à large cycle par procédé multi étagé avec le but de : (1) purification du mélange en réduisant la fraction des co produits (glucose, CD6-CD8) et (2) fractionnement du mélange pour obtenir des fractions majoritairement enrichies en CD9-CD21 et CD22-CD60. Une simulation mathématique a été appliquée pour sélectionner les stratégies de fractionnement à deux concentrations différentes (1 et 3 g/L). Les résultats obtenus pour une concentration initiale de 1 g/L sont assez intéressant vu que la pureté des cyclodextrines à large cycle dans le rétentat final est de 97%. / This study was devoted to the purification and fractionation of cyclodextrins mixtures by membrane processes (NF, UF). Cyclodextrins CDs are produced in mixture by enzymatic degradation of starch. They are cyclic oligosaccharides containing from 6 to more than 60 glucose units (CD6 to CD60).In a first part, complexation ultrafiltration was applied to separate CD6 and CD7. In this study, different parameters such as the pressure, the stoichiometric ratio between CD and complexing agent and the mass ratio between CD were studied. It seems that these factors could influence the selectivity of separation. Diafiltration with a volume reduction factor of 3 was used, with Igepal as complexing agent, to separate the CD6 and CD7. The obtained results are interesting since after four diafiltrations the CD6 was recovered in the permeate with a purity and yield respectively equal to 86 and 71%.In the second part, we were interested in the fractionation of a crude mixture containing large ring cyclodextrins by a multi stage process in order to: (1) purify the mixture from co products (glucose and CD6-CD8) and (2) fractionate the mixture to obtain fractions predominantly enriched in CD9-CD21 and CD22-CD60. A mathematical simulation predicting the composition of the CD mixture after diafiltration was applied to select the strategy of fractionation at two different concentrations (1 and 3g/L). The results obtained for an initial concentration of 1g /L are quite interesting since the purity of large ring cyclodextrins in the final retentate is 97%.

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Membrane processes can cover a wide range of separation problems [with a specific membrane (membrane structure) required for every problem]. Thus, there are membranes available that differ in their structure and consequently in the functionality. Therefore membrane characterization is necessary to ascertain, which membrane may be used for a certain separation. Membranes of pore size ranging from 100nm to 1μm with a uniform pore size are very important in membrane technology. An optimum performance is achieved when the membrane is as thin as possible having a uniform pore size. Here in this thesis, membranes were synthesized by particle assisted wetting using mono-layers of silica colloids as templates for pores along with polymerizable organic liquids on water surface. The pore size reflects the original shape of the particles. Thus it is possible to tune the pore size by varying the particle size. This method is effective to control pore sizes of membranes by choosing silica particles of suitable size. This approach gives a porous structure that is very thin, but unfortunately limited in mechanical stability. Thus there is a need for support which is robust and can withstand the various mechanical stresses. A small change in the membrane or defect in the layered structure during the membrane formation can have drastic effect on the assembly. Lateral homogeneity of the layer generated by the particle assisted wetting can be judged by examination of its reflectivity, but once it is transferred on any solid support this option is no more. So a method is needed to detect the cracks or the inhomogenity of the membrane which can be detected even after the transfer. To tackle this problem a very simple and novel technique for characterizing the membrane by fluorescence labeling and optical inspection was developed in this thesis. The idea was to add a fluorescent dye which is poorly water soluble to the spreading solution comprising of the particles and the monomer. If the dye survived the photo-cross linking, then it would be embedded in the cross-linked polymer and would serve as a marker. Defects and inhomogenity would show up as cracks and spots. By the method that we have developed, we can detect our membrane from the support and spot defects.

Gas separation with polymer membranes are becoming one of the mainstream separation techniques for a myriad of industrial applications. Membrane technologies are recognized as a viable and economical unit operation compared to more conventional separation processes. The design and material selection of membrane separation processes depends highly on the transport properties of separated gas molecules within the membrane material. Therefore, to use efficient methods for gas membrane characterization is paramount for the proper design of membrane separation processes. A membrane can be typically characterized by three main properties: permeability, solubility and diffusivity. The permeability of a membrane is the product of its diffusivity and solubility, therefore obtaining two of the three parameters is sufficient to fully characterize a membrane. The time-lag method is one of the oldest and most used gas membrane characterization methods. However, it suffers from various limitations that make the method not applicable for many types of membranes. The focus in this study was to develop new gas membrane characterization techniques that are based on extracting the membrane properties from the upstream gas pressure measurements rather than only from the downstream pressure measurements. It is believed that characterizing the membrane based on the upstream pressure measurements would be highly useful in characterizing barrier materials which are usually difficult to characterize using the conventional time-lag method. Moreover, glassy polymers which are widely used in industry exhibit behavior associated with nonlinear sorption isotherms and, therefore, the conventional time-lag method is incapable of obtaining an accurate estimation of glassy polymer properties. As a result, sorption experiments to generate a sorption isotherm are usually required in addition to permeation experiments to fully characterize glassy polymer membranes. To quantify the errors associated with the conventional time-lag assumptions and to fundamentally comprehend the impact of nonlinearities on the time-lag method, a comprehensive numerical investigation has been undertaken using the finite difference method. The investigation has clearly put in evidence the effect of the various Langmuir parameters on the accuracy of the time lag and on the time required to achieve steady state. This investigation also allowed assessing the errors associated with the usual assumptions made on the boundary conditions in determining the time lag. In this study, three novel gas membrane characterization methods were developed and proposed. Two of the proposed methods are concerned with the characterization of membranes that can be represented with a linear sorption isotherm. These two methods are entirely based on the upstream pressure measurements. The third membrane characterization method that is proposed is based on the dynamic monitoring of both upstream and downstream pressure measurements and is applicable to systems that exhibit a nonlinear isotherm sorption behavior. The three proposed methods are promising and further experimental validation is recommended to determine their full range of applicability.