31 |
Contribution à l’étude du vieillissement de membranes échangeuses d’ions utilisées dans les procédés d’électrodialyse pour l’industrie agroalimentaire / Contribution to the study of aging of ion exchange membranes used in the electrodialysis process for the food industryGhalloussi-Alloui, Rim 05 December 2012 (has links)
Une étude comparative des caractéristiques statiques, dynamiques et structurale a été menée sur 8 membranes échangeuses d'ions (MEIs), 4 neuves (MEIN) et les mêmes usagées (MEIU) après 2 ans de fonctionnement en ED dans l'industrie agroalimentaire. L'objectif essentiel était de mieux connaître les mécanismes de vieillissement in situ. Nous avons donc mesuré pour chacune de ces MEIs la capacité d'échange, la teneur en eau, la perméabilité ionique, la conductivité électrique, le nombre de transport, l'angle de contact, le courant limite, le module d'Young et la résistance à la traction. Aussi, nous avons effectué des analyses d'IRTF, de MEB et d'EDX. Cette étude nous a permis de conclure que (i) la MEC2 est restée presque stable après les 2 ans d'ED, alors que la MEA1 s'est très fortement dégradée. D'une manière générale, les MEAs sont plus sensibles au vieillissement que les MECs, (ii) les sites fonctionnels sulfoniques s'éliminent de la MEC. Nous ne pouvons pas affirmer ce mécanisme dans le cas des MEAs, mais nous soupçonnons un phénomène d'empoisonnement des sites fonctionnels, (iii) les MEAs se colmatent en surfaces avec des ampleurs différentes entre la MEA1 et la MEA2 / A comparative study of static characteristics, dynamic and structural was conducted on 8 ion-exchange membranes (MEIS), 4 new (IEMN) and the same used (IEMU) after two years of ED operation in the food industry. The main objective was to better understand the mechanisms of in situ ageing. We therefore measured for each IEMs exchange capacity, water content, ionic permeability, electrical conductivity, transport number, contact angle, current limit, Young's modulus and tensile strength. Therefore, we performed analysis of FTIR, SEM and EDX. This study concluded that (i) CEM2 remained almost stable after 2 years of ED, while AEM1 has sharply deteriorated. In general, the AEMs are more susceptible to ageing than CEMs, (ii) the sulfonic functional sites are eliminated from the CEMs. We cannot confirm this mechanism in the case of AEMs, but we suspect a poisoning phenomenon of functional sites, (iii) the AEMs fouled in surfaces with different degrees between AEM1 and AEM2
|
32 |
Etude du décolmatage, par procédés chimiques et biologiques, des membranes échangeuses d'ions utilisées en électrodialyse dans le domaine agroalimentaire / Cleaning study of ion-exchange membranes used in electrodialysis for food industry by chemical and biological processesBdiri, Myriam 30 October 2018 (has links)
L’électrodialyse (ED) est principalement basée sur l’action spécifique des membranes échangeuses d’ions (MEIs) et est largement répandue en industrie agroalimentaire pour la stabilisation tartrique des vins, la désacidification et le traitement des jus de fruits, la déminéralisation du lactosérum ou l’élimination et le fractionnement des protéines du lait. Le colmatage organique, accentué par la complexité de composition des effluents alimentaires et leur richesse en composés phénoliques, représente un facteur majeur de limitation de l’efficacité des procédés et des performances des MEIs. Ce phénomène provoque une diminution de la sélectivité de membranes, une augmentation de leur résistance électrique et réduit le rendement énergétique du procédé conduisant à des pertes économiques en industrie. Cette étude consiste principalement à étudier le décolmatage de MEIs par procédés chimiques et biologiques. Des lots de membranes échangeuses de cations (MECs) et d’anions (MEAs) neuves (1 lot de MEC et 1 lot de MEA) et usées (3 lots de MECs et 2 lots de MEAs) à différentes durées d’utilisation en ED dans l’industrie agroalimentaire –application confidentielle- ont été étudiés. L’ensemble des échantillons ont préalablement été caractérisés pour détermination des paramètres physicochimiques (capacité d’échange (CE), épaisseur (Tm), conductivité électrique (km), angle de contact (θ), teneur en eau (WC) ainsi que la fraction volumique de la solution inter-gel (f2) résultant de l’exploitation du modèle microhétérogène), de structure et morphologiques par spectroscopie IR-TF, microscopie optique, microscopie électronique à balayage et mécaniques par essais de traction. Les effets directs et indirects (causés par les opérations de lavage régulières en industrie) du colmatage ainsi que l’anisotropie des propriétés mécaniques de membrane ont été mis en évidence. Des méthodes de nettoyage non agressives et respectueuses de l’environnement ont été expérimentées en mode statique en ex-situ : Solutions salines (NaCl à 35 g.L-1 et eau de mer reconstituée), solution hydro-alcoolique (mélange eau-éthanol 12%, pH=3,5) et solutions biologique utilisant 3 catégories d’agents enzymatiques (Rohalase BX-BXL, β-glucanase / Corolase 7089, endo-peptidase / Tyrosinase, polyphenol-oxydase) dont les conditions opératoires d’activité enzymatiques optimale ont été déterminées. L’évolution de CE, km, θ et f2 ont été suivis en fonction de la durée de nettoyage. Les solutions salines ont un effet négligeable sur le nettoyage en profondeur mais restent efficaces pour le nettoyage de surface. Cependant, l’application de la solution hydro-alcoolique et des solutions d’enzymes se sont avérées être efficaces pour le décolmatage interne et externe et parviennent à rétablir significativement les paramètres suivis. Il a été démontré que les composés phénoliques, principaux constituants des effluents traités, sont en majeure partie responsables du colmatage des MEIs. Ceux-ci forment des nanoparticules colloïdales denses, non perméables aux ions dans les méso- et macropores des MEIs et ne pénètrent pas dans ses micropores. Une modification du modèle microhétérogène selon cette hypothèse a permis de fournir une interprétation adéquate du km et de modéliser la modification structurale de la phase inter-gel engendrée par les mécanismes de colmatages de polyphénols et expliquer les raisons de diminution du facteur f2app. Une méthode d’extraction utilisant un mélange de solvants (25%V/V, acétone/méthanol/isopropanol/eau) a été mise au point et a permis d’extraire certains composés phénoliques de différents lots de MECs et MEAs usées et ont été identifiés par chromatographie liquide à haute performance. Il a été démontré que les interactions entre les composés phénoliques et la matrice polymère étaient principalement régies par l’empilement des cycles aromatiques et des interactions électrostatiques du type CH-pi et pi-pi ainsi que les liaisons hydrogènes / Conventional electrodialysis (ED) is mainly based on the specific action of ion exchange membranes (IEMs) and is widely used in food industry for tartaric stabilization of wines, deacidification and treatment of fruit juices, demineralization of whey or elimination and fractionation of milk proteins. The organic fouling, accentuated by the complex composition of the food effluents and their richness in phenolic compounds, represents a major limitative factor of the process efficiency and the IEMs performance. This phenomenon causes a decrease in the selectivity of membranes, an increase in their electrical resistance and reduces the energy efficiency of the process leading to economic losses in industry. This study mainly consists in studying the IEMs cleaning by chemical and biological methods. Two batches of new membranes (cation- (CEMs) and anion-exchange membranes (AEMs)) and five batches of used ones (3 CEMs and 2 AEM) with different durations of use in ED units in food industry -confidential application- have been studied. All the samples have been previously characterized to determine their physicochemical parameters (ion-exchange capacity (IEC), thickness (Tm), electrical conductivity (km), contact angle (θ), water content (WC) and the volume fraction of the inter-gel solution (f2) resulting from the study of the micro heterogeneous model), structure and morphology by FTIR spectroscopy, optical microscopy, scanning electron microscopy and mechanical by tensile strength tests. The direct and indirect effects (caused by the regular cleaning operations in industry) of fouling as well as the anisotropy of the membranes mechanical properties have been highlighted. Non-aggressive and environmentally friendly cleaning methods have been experimentally tested in ex-situ static mode: Saline solutions (35 g.L-1 NaCl and reconstituted seawater), hydro-alcoholic solution (12% water-ethanol mixture, pH = 3,5) and biological solutions using 3 categories of enzymatic agents (Rohalase BX-BXL, β-glucanase / Corolase 7089, endo-peptidase / Tyrosinase, polyphenol oxidase) whose operating conditions of optimal enzymatic activity have been determined. The evolution of IEC, km, θ and f2 were followed in function of the cleaning duration. Saline solutions have a negligible effect on intern cleaning but remain efficient for extern cleaning. However, the application of the hydro-alcoholic solution and enzyme solutions have been found to be efficient for both intern and extern cleaning and led to significant recoveries of the studied parameters. It has been shown that phenolic compounds, the principal constituents of treated effluents, are mainly responsible for MEIs fouling. Apparently, they form dense colloidal nanoparticles not permeable for ions within membrane meso- and macropores, not penetrating into micropores. A modification of the micro heterogeneous model under this assumption allowed an adequate interpretation of km and the modelization of structural modifications of the inter-gel phase generated by the fouling mechanisms by polyphenols and explained the reasons why the f2app decreases. An extraction method using a mixture of solvents (25% V/V, acetone/methanol/ isopropanol/water) was developed and made it possible to extract certain phenolic compounds from different batches of used CEMs and AEMs that were identified by high performance liquid chromatography. It has also been demonstrated that the interactions between the phenolic compounds and the polymer matrix are mainly governed by the stacking of aromatic rings and electrostatic interactions of the CH-pi and pi-pi type as well as the hydrogen bonds
|
33 |
Desenvolvimento de membranas de polissulfona para imobilização de lipaseSouza, Jadison Fabricio de 23 August 2006 (has links)
Este trabalho teve por objetivo a preparação e caracterização de membranas de polissulfona (PSU) e a imobilização da enzima lipase nestes filmes, para a produção de membranas enantiosseletivas, visando utilização futura em separação de misturas quirais. Membranas de PSU foram preparadas pelo processo de inversão de fase, utilizando clorofórmio como solvente e água como agente coagulante para a inversão. Foram preparadas membranas com diferentes espessuras e os seguintes parâmetros para a inversão de fase foram definidos: concentração das soluções, tempo de evaporação do solvente, secagem e tratamento térmico. As membranas foram caracterizadas, visando a utilização em processo de eletrodiálise (ED) e imobilização da enzima lipase PS. Para a imobilização foi utilizado o glutaraldeído como agente bifuncional para ligação da enzima ao polímero. Na imobilização foram determinados os parâmetros cinéticos velocidade máxima (Vmáx) e constante de Michaelis-Menten (Km), a quantidade de enzima imobilizada nas membranas pelo método de Bradford e a atividade da enzima livre e imobilizada através da hidrólise do acetato de p-nitrofenila (PNPA). As membranas de PSU preparadas por inversão são hidrofóbicas, e apresentaram características de permesseletividade e capacidade de troca iônica inferiores às apresentadas pelas membranas comerciais Selemion®; CMT e CMV e resistência elétrica superior à destas membranas. O diâmetro dos poros nas membranas é menor que 100 nm. . A quantidade máxima de enzima imobilizada foi de 2,35 mg .g-1 de polímero em 18 horas de imobilização com um rendimento de 61,2%. A atividade da enzima decai após a imobilização, de 14780 U.g-1 (enzima livre) para 1184 U.g-1 (enzima imobilizada). / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-05-13T17:21:10Z
No. of bitstreams: 1
Dissertacao Jadison Fabricio de Souza.pdf: 3168334 bytes, checksum: ec62af877268ce2e7d357db5c8c5e372 (MD5) / Made available in DSpace on 2014-05-13T17:21:10Z (GMT). No. of bitstreams: 1
Dissertacao Jadison Fabricio de Souza.pdf: 3168334 bytes, checksum: ec62af877268ce2e7d357db5c8c5e372 (MD5) / Preparation and characterization of polysulfone (PSU) membranes and the immobilization of lipase enzyme in these membranes to produce enantioselective membranes, in order to separate chiral compounds, is the subject of the present work. PSU membranes were prepared by phase inversion, using chloroform as solvent and water as nonsolvent. Membranes with different thickness were prepared and phase inversion parameters such as (solution concentrations, solvent evaporation time, drying and thermal treatment) were investigated. Membranes were characterized, in order to use them in electrodialysis process (ED) and in the lipase PS enzyme immobilization. For immobilization, bifunctional agent glutaraldehyde was used to link the enzyme to the polymer. On immobilization, the kinetic constants (Km e Vmax), the amount of immobilized enzyme with Bradford method and the activity of free and immobilized enzyme with p-nitrophenyl acetate (PNPA) hydrolysis, were determined. PSU membranes prepared by phase inversion are hydrophobic and, when compared with Selemion®; CMT and CMV commercial membranes, present lower permeselectivity, lower ion exchange capability and higher resistance. Membranes pore diameter is lower than 100 nm. The maximum amount of immobilized enzyme in the membranes reached 2.35 mg per gram of polymer after 18 hours of immobilization with a 61,2% yield . Enzyme activity decays after immobilization , from 14780 U.g-1 (free enzyme) to 1184 U.g-1 (immobilized enzyme).
|
34 |
Desenvolvimento de membranas de polissulfona para imobilização de lipaseSouza, Jadison Fabricio de 23 August 2006 (has links)
Este trabalho teve por objetivo a preparação e caracterização de membranas de polissulfona (PSU) e a imobilização da enzima lipase nestes filmes, para a produção de membranas enantiosseletivas, visando utilização futura em separação de misturas quirais. Membranas de PSU foram preparadas pelo processo de inversão de fase, utilizando clorofórmio como solvente e água como agente coagulante para a inversão. Foram preparadas membranas com diferentes espessuras e os seguintes parâmetros para a inversão de fase foram definidos: concentração das soluções, tempo de evaporação do solvente, secagem e tratamento térmico. As membranas foram caracterizadas, visando a utilização em processo de eletrodiálise (ED) e imobilização da enzima lipase PS. Para a imobilização foi utilizado o glutaraldeído como agente bifuncional para ligação da enzima ao polímero. Na imobilização foram determinados os parâmetros cinéticos velocidade máxima (Vmáx) e constante de Michaelis-Menten (Km), a quantidade de enzima imobilizada nas membranas pelo método de Bradford e a atividade da enzima livre e imobilizada através da hidrólise do acetato de p-nitrofenila (PNPA). As membranas de PSU preparadas por inversão são hidrofóbicas, e apresentaram características de permesseletividade e capacidade de troca iônica inferiores às apresentadas pelas membranas comerciais Selemion®; CMT e CMV e resistência elétrica superior à destas membranas. O diâmetro dos poros nas membranas é menor que 100 nm. . A quantidade máxima de enzima imobilizada foi de 2,35 mg .g-1 de polímero em 18 horas de imobilização com um rendimento de 61,2%. A atividade da enzima decai após a imobilização, de 14780 U.g-1 (enzima livre) para 1184 U.g-1 (enzima imobilizada). / Preparation and characterization of polysulfone (PSU) membranes and the immobilization of lipase enzyme in these membranes to produce enantioselective membranes, in order to separate chiral compounds, is the subject of the present work. PSU membranes were prepared by phase inversion, using chloroform as solvent and water as nonsolvent. Membranes with different thickness were prepared and phase inversion parameters such as (solution concentrations, solvent evaporation time, drying and thermal treatment) were investigated. Membranes were characterized, in order to use them in electrodialysis process (ED) and in the lipase PS enzyme immobilization. For immobilization, bifunctional agent glutaraldehyde was used to link the enzyme to the polymer. On immobilization, the kinetic constants (Km e Vmax), the amount of immobilized enzyme with Bradford method and the activity of free and immobilized enzyme with p-nitrophenyl acetate (PNPA) hydrolysis, were determined. PSU membranes prepared by phase inversion are hydrophobic and, when compared with Selemion®; CMT and CMV commercial membranes, present lower permeselectivity, lower ion exchange capability and higher resistance. Membranes pore diameter is lower than 100 nm. The maximum amount of immobilized enzyme in the membranes reached 2.35 mg per gram of polymer after 18 hours of immobilization with a 61,2% yield . Enzyme activity decays after immobilization , from 14780 U.g-1 (free enzyme) to 1184 U.g-1 (immobilized enzyme).
|
35 |
Membrane Processes for Sustainable Energy ApplicationsPatil, Rahul January 2012 (has links)
No description available.
|
36 |
Solvation-Driven Actuation of Anion-Exchange MembranesUlbricht, Nicco, Boldini, Alain, Bae, Chulsung, Wallmersperger, Thomas, Porfir, Maurizio 11 June 2024 (has links)
Ion-exchange membranes, conventionally utilized in separation processes of electrolyte solutions, are electroactive polymers that display a unique coupling between electrochemistry and mechanics. Previous experimental studies have demonstrated the possibility of actuating cation-exchange membranes in salt solution through the application of a remote external electric field. The use of anion-exchange membranes as contactless actuators, however, has never been documented and little is known about the physics of their actuation. Here, it is reported for the first time the possibility of contactless actuating anion-exchange membranes in salt solutions; such an actuation is mediated by the selection of anions in the external salt solution and the membrane. Actuation is attributed to the physical phenomenon of solvation, the interaction between ions and solvent in solution. Contrary to previous studies with cation-exchange membranes, the results show that anion-exchange membranes consistently bend toward the anode. The integration of anion-exchange and cation-exchange membranes in composites promises innovative programmable contactless actuators, with applications in underwater robotics and biomedical engineering.
|
37 |
Linear and Nonlinear Viscoelastic Characterization of Proton Exchange Membranes and Stress Modeling for Fuel Cell ApplicationsPatankar, Kshitish A. 20 August 2009 (has links)
In this dissertation, the effect of temperature and humidity on the viscoelastic and fracture properties of proton exchange membranes (PEM) used in fuel cell applications was studied. Understanding and accurately modeling the linear and nonlinear viscoelastic constitutive properties of a PEM are important for making hygrothermal stress predictions in the cyclic temperature and humidity environment of operating fuel cells. In this study, Nafion® NRE 211, Gore-Select® 57, and Ion Power® N111-IP were characterized under various humidity and temperature conditions. These membranes were subjected to a nominal strain in a dynamic mechanical analyzer (DMA), and their stress relaxation behavior was characterized over a period of time. Hygral master curves were constructed noting hygral shift factors, followed by thermal shifts to construct a hygrothermal master curve. This process was reversed (thermal shifts followed by hygral shifts) and was seen to yield a similar hygrothermal master curve. Longer term stress relaxation tests were conducted to validate the hygrothermal master curve. The Prony series coefficients determined based on the hygrothermal stress relaxation master curves were utilized in a linear viscoelastic stress model.
The nonlinear viscoelastic behavior of the membranes was characterized by conducting creep tests on uniaxial tensile specimens at various constant stress conditions and evaluating the resulting isochronal stress-strain plots. The nonlinearity was found to be induced at relatively moderate stress/strain levels under dry conditions. To capture the nonlinearity, the well known Schapery model was used. To calculate the nonlinear parameters defined in the Schapery model, creep/recovery tests at various stress levels and temperatures were performed. A one-dimensional Schapery model was developed and then validated using various experiments.
The fracture properties were studied by cutting membranes using a sharp knife mounted on a specially designed fixture. Again, various temperature and humidity conditions were used, and the fracture energy of the membranes was recorded as a function of cutting rate. Fracture energy master curves with respect to reduced cutting rates were constructed to get some idea about the intrinsic fracture energy of the membrane. The shift factors obtained from the fracture tests were found to match with those obtained from the stress relaxation experiments, suggesting that the knife cutting process is viscoelastic in nature. The rate and temperature dependence for these fracture energies are consistent with the rate, temperature, and moisture dependence of the relaxation modulus, suggesting the usefulness of a viscoelastic framework for examining and modeling durability of fuel cell membranes. The intrinsic fracture energy was initially thought to be a differentiating factor, which would separate various membranes tested in this study from one another. However, it was later found that all the membranes tested showed similar values at lower cutting rates, but showed significant variation at higher reduced cutting rates, and thus was thought to be a more meaningful region to differentiate the membranes for durability understanding.
While the preceding work was undertaken to characterize as-received commercial PEMs, it is possible to modify material properties through treatment processes including thermal annealing and water treatment. The transient and dynamic viscoelastic properties of water-treated Nafion membranes revealed unusual behavior. Such unusual properties might have originated from irreversible morphological changes in PEM. Besides the constitutive viscoelastic properties, another set of properties useful for the stress modeling is the hygral strain induced as a function of relative humidity (RH) The effect of pretreatment on hygral strains induced as a function of RH was also investigated. These studies suggest that pretreatment significantly changes the mechanical properties of proton exchange membranes. / Ph. D.
|
38 |
Synthesis and Characterization of Multiblock Copolymers for Proton Exchange Membrane Fuel Cells (PEMFC)Wang, Hang 25 January 2007 (has links)
Nanophase-separated hydrophilic-hydrophobic multiblock copolymers are promising proton exchange membrane (PEM) materials due to their ability to form various morphological structures which enhance transport.
Four arylene chlorides monomers (2,5-Dichlorobenzophenone and its derivatives) were first successfully synthesized from aluminum chloride-catalyzed, Friedel-Crafts acylation of benzene and various aromatic compounds with 2,5-dichlorobenzoyl chloride. These monomers were then polymerized via Ni (0)-catalyzed coupling reaction to form various high molecular weight substituted poly(2,5-benzophenone)s. Great care must be taken to achieve anhydrous and inert conditions during the reaction.
A series of poly(2,5-benzophenone) activated aryl fluoride telechelic oligomers with different block molecular weights were then successfully synthesized by Ni (0)- catalyzed coupling of 2,5-dichloro-benzophenone and the end-capping agent 4-chloro-4'-fluorobenzophenone or 4-chlorophenly-4′-fluorophenyl sulfone. The molecular weights of these oligomers were readily controlled by altering the amount of end-capping agent. These telechelic oligomers (hydrophobic) were then copolymerized with phenoxide terminated disulfonated poly (arylene ether sulfone)s (hydrophilic) by nucleophilic aromatic substitution to form novel hydrophilic-hydrophobic multiblock copolymers.
A series of novel multiblock copolymers with number average block lengths ranging from 3,000 to 10,000 g/mol were successfully synthesized. Two separate Tgs were observed via DSC in the transparent multiblock copolymer films when each block length was longer than 6,000 g/mol (6k). Tapping mode atomic force microscopy (AFM) also showed clear nanophase separation between the hydrophilic and hydrophobic domains and the influence of block length, as one increased from 6k to 10k. Transparent and creasable films were solvent-cast and exhibited good proton conductivity and low water uptake.
These PAES-PBP multiblock copolymers also showed much less relative humidity (RH) dependence than random sulfonated aromatic copolymers BPSH 35 in proton conductivity, with values that were almost the same as Nafion with decreasing RHs. This phenomenon lies in the fact that this multiblock copolymer possesses a unique co-continuous nanophase separated morphology, as confirmed by AFM and DSC data. Since this unique co-continuous morphology (interconnected channels and networks) dramatically facilitates the proton transport (increase the diffusion coefficient of water), improved proton conductivity under partially hydrated conditions becomes feasible. These multiblock copolymers are therefore considered to be very promising candidates for high temperature proton exchange membranes in fuel cells. / Ph. D.
|
39 |
Evaluation of Electrochemical Storage Systems for Higher Efficiency and Energy DensityMartino, Drew J 25 January 2017 (has links)
Lack of energy storage is a key issue in the development of renewable energy sources. Most renewables, especially solar and wind, when used alone, cannot sustain a reliably constant power output over an extended period of time. These sources generally generate variable amounts of power intermittently, therefore, an efficient electrical energy storage (EES) method is required to better temporally balance power generation to power consumption. One of the more promising methods of electrical energy storage is the unitized regenerative fuel cell (UFRC.) UFRCs are fuel cells that can operate in a charge-discharge cycle, similar to a battery, to store and then to subsequently release power. Power is stored by means of electrolysis while the products of this electrolysis reaction can be recombined as in a normal fuel cell to release the stored power. A major advantage of UFRCs over batteries is that storage capacity can be decoupled from cell power, thus reducing the potential cost and weight of the cell unit. Here we investigate UFRCs based on hydrogen-halogen systems, specifically hydrogen-bromine, which has potential for improved electrode reaction kinetics and hence cheaper catalysts and higher efficiency and energy density. A mathematical model has been developed to analyze this system and determine cell behavior and cycle efficiency under various conditions. The conventional H2-Br2 URFCs, however also so far have utilized Pt catalysts and Nafion membranes. Consequently, a goal of this work was to explore alternate schemes and materials for the H2-Br2 URFC. Thus, three generations of test cells have been created. The first two cells were designed to use a molten bromide salt, ionic liquid or anion exchange membrane as the ion exchange electrolyte with the liquids supported on a porous membrane. This type of system provides the potential to reduce the amount of precious metal catalyst required, or possibly eliminate it altogether. Each cell showed improvement over the previous generation, although the results are preliminary. The final set of results are promising for anion exchange membranes on a cost basis compared Nafion. Another promising energy storage solution involves liquid methanol as an intermediate or as a hydrogen carrier. An alternative to storing high-pressure hydrogen is to produce it on-board/on-site on demand via a methanol electrocatalytic reformer (eCRef), a PEM electrolyzer in which methanol-water coelectrolysis takes place. Methanol handling, storage, and transportation is much easier than that for hydrogen. The hydrogen produced via methanol eCref may then be used in any number of applications, including for energy storage and generation in a standard H2-O2 PEM fuel cell. The mathematical modeling and analysis for an eCref is very similar to that of the HBr URFC. In this work, a comprehensive model for the coelectrolysis of methanol and water into hydrogen is created and compared with experimental data. The performance of the methanol electrolyzer coupled with a H2-O2 fuel cell is then compared for efficiency to that of a direct methanol fuel cell data and was found to be superior. The results suggest that an efficient and small paired eCRef-fuel cell system is potentially be a cheaper and more viable alternative to the standard direct methanol fuel cell. Both the H2-Br2 URFC and the methanol eCref in combination with a H2-O2 fuel cell have significant potential to provide higher energy efficiency and energy density for EES purposes.
|
40 |
Atomistic and molecular simulations of novel acid-base blend membranes for direct methanol fuel cellsMahajan, Chetan Vasant 04 February 2014 (has links)
One of the main challenges to transform highly useful Direct Methanol Fuel Cells (DMFC) into a commercially viable technology has been to develop a low cost polymer electrolyte membrane (PEM) with high proton conductivity, high stability and low methanol crossover under operating conditions desirably including high temperatures. Nafion, the widely used PEM, fails to meet all of these criteria simultaneously. Recently developed acid-base polymer blend membranes constitute a promising class of PEMs alternative to Nafion on above criteria. Even though some of these membranes produce better performance than Nafion, they still present numerous opportunities for maximizing high temperature proton conductivity and dimensional stability with concomitant minimization of methanol crossover. Our contribution embarks on the fundamental study of one such novel class of blend membranes viz., sulfonated poly (ether ether ketone) (SPEEK)(95 % by weight) blended with polysulfone tethered with base (5 % by weight) such as 2-aminobenzimidazole (ABIm), 5-amino-benzotriazole (BTraz) and 1H-perimidine (PImd), developed by Manthiram group at The University of Texas at Austin.
In this work, we report extensive all-atom classical as well as ab-initio molecular dynamics (MD) simulations of such water-methanol solvated blend membranes (as well as pure SPEEK and Nafion) the first time. Our approach consists of three steps: (1) Predict dynamical properties
such as diffusivities of water, methanol and proton in such membranes (2) Validate against experiments (3) Develop understanding on the
interplay between basic chemistry, structure and properties, the knowledge that can potentially be used to develop better candidate membranes.
In particular, we elucidate the impact of simple, fundamental physiochemical features of the polymeric membranes such as hydrophilicity,
hydrophobicity, structure or the size of the base on the structural manifestations on the bigger scale such as nanophase segregation, hydrogen bonding or pore sizes, which ultimately affect the permeant transport through such systems. / text
|
Page generated in 0.1761 seconds