The anisotropic mass transport issues inside a fuel cell membrane have been studied in this thesis using computer modelling. The polymer electrolyte membrane (PEM) conductivity of a PEM fuel cell (PEMFC) depends on the hydration state of the hydrophilic charged sites distributed in the pores of the membrane. Water humidification of these charged sites is crucial for sustaining the membrane conductivity and reducing concerning voltage losses of the cell. During the operation of a PEMFC, the transport of humidified inlet gases (fuel/oxidant) is influenced by external design factors such as flow field plate geometry of the gas circulating channels. As a result, there arises a distribution in the mass transport of water inside the membrane electrode assembly. A two-dimensional, cross-the-channel, fuel cell membrane layer mass transport model, developed in this work, helps the study of the impact of factors causing the distribution in the membrane ionic conductivity on ohmic losses.<p>The governing equations of the membrane mathematical model stem from the multicomponent framework of concentrated solution theory. All mass transport driving forces within the vapour and/or liquid equilibrated phases have been accounted in this research. A computational model, based on the finite control volume method, has been implemented using a line-by-line approach for solving the dependent variables of the mass transport equations in the two-dimensional membrane domain. The required boundary conditions for performing the anisotropic mass transport analysis have been obtained from a detailed agglomerate model of the cathode catalyst layer available in the literature.<p>The results obtained using boundary conditions with various flow field plate channel-land configurations revealed that the anisotropic water transport in the cathode half-cell severely affects the ohmic losses within the membrane. A partially humidified vapour equilibrated membrane simulation results show that a smaller channel-land ratio (1:1) sustains a better membrane performance compared to that with a larger one (2:1 or 4:1). Resistance calculations using the computer model revealed that ohmic losses across the membrane also depend on its physical parameters such as thickness. It was observed that the resistance offered by a thinner membrane towards vapour phase mass transport is comparatively lower than that offered by a thicker membrane. A further analysis accounting the practical aspects such as membrane swelling constraints, imposed by design limitations of a fuel cell, revealed that the membrane water content and ionic conductivity are altered with an increase in the compression constraint effects acting upon a free swelling membrane.

Thesis (Ph. D.)--Case Western Reserve University, 2004. / [School of Medicine] Department of Pathology. Includes bibliographical references. Available online via OhioLINK's ETD Center.

Thesis (Ph. D.)--University of Washington, 2003. / Vita. Includes bibliographical references (leaves 96-104).

Anaerobic membrane bioreactors may provide a sustainable technological solution for digestion of waste activated sludge due to their capacity to achieve substantial volatile solids (VS) destruction and positive energy balances with reduced digester volumes. However, membrane integrated anaerobic systems may have limitations that are imposed by membrane fouling and a decrease in biomass activity due to possible exposure of biomass to high shear conditions. This study characterised bioprocess and membrane performance under varying conditions, identified foulant type and origin and mechanism of fouling, and developed fouling control strategies by using low cross flow velocity and pressure anaerobic membrane systems. The study employed a pilot scale anaerobic digester integrated with negative and neutral tubular membranes; pilot and bench scale control digesters supported with bench scale filtration unit parametric studies. The membranes were polyvinylidene difluoride based with an average pore size of 0.02 micron and were operated at a constant cross flow velocity of 1 ms-1 and constant trans-membrane pressure of 30 kPa. Four operating conditions consisting of different combinations of HRT and SRT were evaluated. By integrating membranes into the digesters it was possible to simultaneously enhance digestion and increase throughput of the digesters without affecting its performance. The anaerobic membrane digester showed 48-49% volatile solids destruction at 30 days SRT under conventional and higher loadings of 1.2±0.4 and 2.1±0.6 kg COD m-3day-1. This was a 100% increase in performance compared to a control digester subjected to higher loading. This result was supported by the associated specific methane generation. The control digesters operated at a relatively higher SRT showed comparable VS destruction and gas generation to the anaerobic membrane running at a similar SRT. However the extra gas generated didn’t compensate heat required to maintain larger volume of the digester. In case of anaerobic membrane digesters due to the high rate feeding, increase biogas production and co-thickening, the energy balance increased by 144 and 200% under conventional and higher loading conditions respectively. Characterization of membrane performance showed that the average sustainable flux was 23.2±0.4 and 14.8±0.4 LMH during HRT-SRTs of 15-30 and 7-15 days respectively. The critical fluxes were in the range of 30-40, 16-17 and 20-22 LM-2H-1 during HRT-SRTs of 15-30, 7-30 and 7-15 days respectively. The decline in membrane performance at a higher loading was associated with the formation of cake layers on the membrane surface that led to reversible fouling. The additional decline in performance at extended SRT was attributed to irreversible fouling. The colloidal fraction of the sludge showed an overall higher fouling propensity during the long term pilot studies and short term filtration tests. The suspended solids fraction of the sludge showed a positive impact at concentration below 15 g/L but resulted in a decrease of membrane performance at higher concentrations. Further studies of foulant origin through a series of microscopic, membrane cleaning and sludge characterization studies showed that the colloidal proteins, soluble carbohydrates and inorganic materials such as iron, calcium and sulfur and their interaction to have a significant impact on membrane fouling. To control anaerobic membrane fouling by the digested sludge, integration of membrane relaxation techniques in the filtration cycle were found effective. By incorporating a unique relaxation technique to tubular membranes, it was possible to increase the sustainable flux to 29.2±1.8 and 34.5±2.5 LM-2H-1 for neutral and negative membranes during 15-30 HRT-SRT process condition. Addition of cationic polymers and sequential mechanical-citric acid membrane cleaning, that targeted both reversible and irreversible fouling was also found effective.

Membrane fouling is a chronic problem for many nanofiltration (NF) membrane plants. Foulant material can range from colloidal, particulate, inorganic minerals and natural organic matter (NOM) (Schäfer et al., 2006). This research project worked with a small community integrated membrane facility (low-pressure membrane followed by high-pressure) in Nova Scotia with membrane fouling concerns associated with dissolved NOM as the primary foulant. Membrane autopsies conducted in our laboratory have demonstrated that NOM deposits on the NF membrane decreased pore space on the membrane (Lamsal et al., 2012). The membrane fouling resulted in a requirement for increased pressure to produce a constant permeate flow. By adding in-line coagulation prior to low-pressure filtration in an integrated membrane system, the goal was to remove more organic material by MF thereby improving the quality of the feed-water entering the NF membranes. Previous work has shown that for some IMS installations there is a need to reduce the amount of dissolved organic matter prior to NF (Cho et al., 2000; Lamsal et al., 2012; Nilson and DiGiano, 1996; Schäfer et al., 2001). An improved membrane feed-water quality reduces fouling on the membrane and membrane operating cost, and increases productivity and lifespan of the membrane (Choi, 2008). A negative aspect to adding in-line coagulation is it adds another step to the treatment process and sludge removal is required. This study examined the use of in-line coagulation using coagulants aluminum sulphate, ferric chloride and polyaluminum chloride to improve membrane feed-water quality. The addition of in-line coagulation prior to microfiltration will remove NOM with the MF producing improved feed water quality for NF. After determining the optimal dose of each coagulant, 20 L of post-coagulation MF permeate was batched and run through the bench-scale NF membrane for 200 hours. The water quality of the feed tank, concentrate and permeate were monitored constantly as well as the operational properties of pressure and flow. To simulate a full-scale plant the operating conditions of Collins Park water treatment plant on Fletchers Lake were used in the bench-scale set-up. After the 200h NF run time the membranes were analyzed to assess the fouling on the membrane and the performance of each coagulant. Coagulation was found to reduce NF pressure fouling by reduction of NOM in the NF feed-water. Ferric chloride was found to perform best of the three coagulants at a low dose of 0.5mg/L of Fe at a pH of 5.0. / n/a

No description available.

Whey protein fractionation is an important industrial process that requires effective large-scale processes. Although packed bed chromatography has been used extensively, it suffers from low processing rates due to high back-pressures generated at high flow rates. Batch chromatography has been applied but generally has a low efficiency. More recently, adsorptive membranes have shown great promise for large-scale protein purification, particularly from large-volume dilute feedstocks. A new method for producing versatile adsorptive membranes by combining membrane and chromatographic resin matrices has been developed but not previously applied to whey protein fractionation. In this work, a series of mixed matrix membranes (MMMs) were developed for membrane chromatography using ethylene vinyl alcohol (EVAL) based membranes and various types of adsorbent resin. The feasibility of MMM was tested in bovine whey protein fractionation processes. Flat sheet anion exchange MMMs were cast using EVAL and crushed Lewatit® MP500 (Lanxess, Leverkusen, Germany) anion resin, expected to bind the acidic whey proteins β-lactoglobulin (β-Lac), α-lactalbumin (α-Lac) and bovine serum albumin (BSA). The MMM showed a static binding capacity of 120 mg β-Lac g⁻¹ membrane (36 mg β-Lac mL⁻¹ membrane) and 90 mg α-Lac g⁻¹ membrane (27 mg α-Lac mL⁻¹ membrane). It had a selective binding towards β-Lac in whey with a binding preference order of β-Lac > BSA > α-Lac. In batch whey fractionation, average binding capacities of 75.6 mg β-Lac g⁻¹ membrane, 3.5 mg α-Lac g⁻¹ membrane and 0.5 mg BSA g⁻¹ membrane were achieved with a β-Lac elution recovery of around 80%. Crushed SP Sepharose™ Fast Flow (GE Healthcare Technologies, Uppsala, Sweden) resin was used as an adsorbent particle in preparing cation exchange MMMs for lactoferrin (LF) recovery from whey. The static binding capacity of the cationic MMM was 384 mg LF g⁻¹membrane or 155 mg LF mL⁻¹ membrane, exceeding the capacity of several commercial adsorptive membranes. Adsorption of lysozyme onto the embedded ion exchange resin was visualized by confocal laser scanning microscopy. In LF isolation from whey, cross-flow operation was used to minimize membrane fouling and to enhance the protein binding capacity. LF recovery as high as of 91% with a high purity (as judged by the presence of a single band in gel electrophoresis) was achieved from 150 mL feed whey. The MMM preparation concept was extended, for the first time, to produce a hydrophobic interaction membrane using crushed Phenyl Sepharose™ (GE Healthcare Technologies, Uppsala, Sweden) resin and tested for the feasibility in whey protein fractionation. Phenyl Sepharose MMM showed binding capacities of 20.54 mg mL⁻¹ of β-Lac, 45.58 mg mL⁻¹ of α-Lac, 38.65 mg mL⁻¹ of BSA and 42.05 mg mL⁻¹ of LF for a pure protein solution (binding capacity values given on a membrane volume basis). In flow through whey fractionation, the adsorption performance of the Phenyl Sepharose MMM was similar to the HiTrap™ Phenyl hydrophobic interaction chromatography column. However, in terms of processing speed and low pressure drop across the column, the benefits of using MMM over a packed bed column were clear. A novel mixed mode interaction membrane was synthesized in a single membrane by incorporating a certain ratio of SP Sepharose cation resin and Lewatit MP500 anion resin into an EVAL base polymer solution. The mixed mode cation and anion membrane chromatography developed was able to bind basic and acidic proteins simultaneously from a solution. Furthermore, the ratio of the different types of adsorptive resin incorporated into the membrane matrix could be customised for protein recovery from a specific feedstream. The customized mixed mode MMM consisting of 42.5 wt% of MP500 anionic resin and 7.5 wt% SP Sepharose cationic resin showed a binding capacity of 7.16 mg α-Lac g⁻¹ membrane, 11.40 mg LF g⁻¹ membrane, 59.21 mg β-Lac g⁻¹ membrane and 6.79 mg IgG g⁻¹ membrane from batch fractionation of 1 mL LF-spiked whey. A tangential flow process using this membrane was predicted to be able to produce 125 g total whey protein per L membrane per h.

Hybrid membranes represent a promising alternative to the limitations of organic and inorganic materials for high productivity and selectivity gas separation membranes. In this study, the previously developed concept of emulsion-polymerized mixed matrix (EPMM) membranes was further advanced by investigating the effects of surfactant and compatibilizer on inorganic loading in poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based EPMM membranes, in which inorganic part of the membranes originated from tetraethylorthosilicate (TEOS). The polymerization of TEOS, which consists of hydrolysis of TEOS and condensation of the hydrolyzed TEOS, was carried out as (i) one- and (ii) two-step processes. In the one-step process, the hydrolysis and condensation take place in the same environment of a weak acid provided by the aqueous solution of aluminum hydroxonitrate and sodium carbonate. In the two-step process, the hydrolysis takes place in the environment of a strong acid (solution of hydrochloric acid), whereas the condensation takes place in weak base environment obtained by adding excess of the ammonium hydroxide solution to the acidic solution of the hydrolyzed TEOS. For both one- and two-step processes, the emulsion polymerization of TEOS was carried out in two types of emulsions made of (i) pure trichloroethylene (TCE) solvent, and (ii) 10 w/v% solution of PPO in TCE, using different combinations of the compatibilizer (ethanol) and the surfactant (n-octanol). The experiments with pure TCE, which are referred to as a gravimetric powder method (GPM) allowed assessing the effect of different experimental parameters on the conversion of TEOS. The GPM tests also provided a guide for the synthesis of casting emulsions containing PPO, from which the EPMM membranes were prepared using a spin coating technique. The synthesized EPMM membranes were characterized using 29Si nuclear magnetic resonance (29Si NMR), differential scanning calorimetry (DSC), inductively coupled plasma mass spectrometry (ICP-MS), and gas permeation measurements carried out in a constant pressure (CP) system. The 29Si NMR analysis verified polymerization of TEOS in the emulsions made of pure TCE, and the PPO solution in TCE. The conversions of TEOS in the two-step process in the two types of emulsions were very close to each other. In the case of the one-step process, the conversions in the TCE emulsion were significantly greater than those in the emulsion of the PPO solution in TCE. Consequently, the conversions of TEOS in the EPMM membranes made in the two-step process were greater than those in the EPMM membranes made in the one-step process. The latter ranged between 10 - 20%, while the highest conversion in the two-step process was 74% in the presence of pure compatibilizer with no surfactant. Despite greater conversions and hence the greater inorganic loadings, the EPMM membranes prepared in the two-step process had glass transition temperatures (Tg) only slightly greater than the reference PPO membranes. In contrast, despite relatively low inorganic loadings, the EPMM membranes prepared in the one-step process had Tgs markedly greater than PPO, and showed the expected trend of an increase in Tg with the inorganic loading. These results indicate that in the case of the one-step process the polymerized TEOS was well integrated with the PPO chains and the interactions between the two phases lead to high Tgs. On the other hand, this was not the case for the EPMM membranes prepared in the two-step process, suggesting possible phase separation between the polymerized TEOS and the organic phase. The latter was confirmed by detecting no selectivity in the EPMM membranes prepared by the two-step process. In contrast, the EPMM membranes prepared in the one-step process in the presence of the compatibilizer and no surfactant showed 50% greater O2 permeability coefficient and a slightly greater O2/N2 permeability ratio compared to the reference PPO membranes.

No description available.

<p>Over the past 40 years, research pertaining to membrane technology has lead to the development of a wide range of applications including beverage production, water purification and the separation of dairy products. For the separation of gases, membrane technology is not as widely applied since the production of suitable gas separation membranes is far more challenging than the production of membranes for eg. water purification. Hydrogen is currently produced by recovery technologies incorporated in various chemical processes. Hydrogen is mainly sourced from fossil fuels via steam reformation and coal gasification. Special attention will be given to Underground Coal Gasification since it may be of great importance for the future of South Africa. The main aim of this study was to develop low temperature CsHSO4/SiO2 composite membranes that show significant Idea selectivity towards H2:CO2 and H2:CH4.</p>