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Optimisation and integration of membrane processes in coal-fired power plants with carbon capture and storageBocciardo, Davide January 2015 (has links)
This thesis investigates membrane gas separation and its application to post-combustion carbon capture from coal-fired power plants as alternative to the conventional amine absorption technology. The attention is initially focused on membrane module modelling, with the aim of obtaining more detailed predictions of the behaviour of the separation though spiral-wound and hollow-fibre modules. Both one- and bi-dimensional models are implemented, compared and tested for different separations. Module geometry is investigated as well as the effect on the performances due to possible fabrication defects. A key part of the work involves the integration of the customised models into UniSim® Design, the Honeywell process simulator. Thanks to the developed interface, multi-stage process designs are developed, compared with the available literature and linked to a rigorous economic analysis. In particular, a long-term indicator such as the Levelised Cost Of Electricity (LCOE) is evaluated and parametric analyses are conducted with respect to both material and process parameters.
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Donor-Acceptor Substituted Triplet Emitters / Donor-Akzeptor substutuierte Triplett-EmitterGeiß, Barbara January 2009 (has links) (PDF)
Im ersten Teil dieser Arbeit wurden die Synthesen und photophysikalischen Eigenschaften mehrerer Donor-Akzeptor-substituierter Übergangsmetallkomplexe des Typs [(C^N)2Ir(N^N)][PF6] vorgestellt. Das Ir(III) wurde mit Lochleitern wie Carbazol (CZ) und Triarylamin (TAA), die über eine Methyl- und Ethylbrücke mit dem cyclometallierten C^N-Liganden Phenylpyrazol (ppz) und Phenylpyridin (ppy) verbunden waren, verknüpft. Zweizähnige neutrale N^N- und P^P-Liganden wie 2,2’-Bipyridyl (bpy), 3,4,7,8-Tetramethyl-1,10-phenanthrolin (tmp) und cis-1,2-Bis(diphenylphosphino)ethylen (bdppe) wurden als Akzeptoren ausgewählt.Um die Eigenschaften in Vergleich setzen zu können, wurden die entsprechenden Referenzverbindungen ohne Lochleiter hergestellt. Alle Carbazol-Komplexe, bis auf die bdppe-Verbindungen, zeigen Emission und transiente Absorption ähnlich denen ihrer Referenzverbindungen, was sie für Anwendungen in der OLED-Forschung interessant macht. Untersuchungen an LECs (lichtemittierende elektrochemische Zellen) zeigen eine rotverschobene Lumineszenz. Die Triarylamin-Komplexe zeigen keine Emission bei RT, allerdings weisen diese eine intensive, blauverschobene und langlebige Lumineszenz bei 77 K in einer festen Matrix auf. Die transienten Absorptionsspektren unterscheiden sich stark von denen der Referenzverbindungen. Sie weisen charakteristische Merkmale von den Spektren der isolierten Radikalanionen und Radikalkationen auf, was durch spektroelektrochemische Messungen bewiesen wurde. Daraus kann geschlossen werden, dass es sich bei dem angeregten Zustand um einen ladungsgetrennten (CS) Zustand handelt, wo die positive Ladung am Triarylamin-Donor und die negative Ladung am N^N-Akzeptor sitzt. Die Abklingzeiten der angeregten Zustände verlaufen biexponentiell, was ein Hinweis auf das Vorhandensein zweier angeregter Zustände, dem 1CS und 3CS Zustand, ist. Um dieses Verhalten zu untersuchen, wurden verschieden substituierte bpy-Komplexe synthetisiert und analysiert. Temperaturabhängige Messungen der transienten Absorption zeigten, dass alle Ratenkonstanten temperaturunabhängig sind, mit Ausnahme des OMe-substituierten Komplexes. Die Gleichgewichtskonstante K = k1 / k2 ist nahezu eins für alle Komplexe. Bei dem OMe-Komplex sinkt sie mit steigender Temperatur. Eine Auftragung der Ratenkonstanten gegen die Energiedifferenzen, die durch cyclovoltammetrische Messungen erhalten wurden, zeigte, dass alle Konstanten mit steigender Donorstärke am bpy-Liganden abfallen. DFT-Rechnungen an der OMe-Verbindung sind noch in Arbeit. Im zweiten Teil dieser Arbeit wurden neutrale Ir(III) und Pt(II) Komplexe des Typs [(O^O)Ir(N^N)2] und [(O^O)Pt(N^N)] vorgestellt. Hier wurde TAA mit Acetylacetonat (acac) direkt, oder über eine CH2-Brücke verbunden, um den Einfluss der Art der Verbrückung auf die photophysikalischen Eigenschaften zu beobachten. Als zweizähniger N^N-Ligand wurde 2,2’-Bipyridyl (bpy) gewählt. Auch hier wurden alle entsprechenden Referenzverbindungen ohne Triarylamin als Vergleich hergestellt. Zudem wurde der homoleptische fac Ir(N^N)3 Komplex mit Triarylamin, welches über eine Methyl- und Ethylbrücke an Phenylpyrazol angeknüpft wurde, synthetisiert. Die Synthese des Ir(III)-Komplexes mit TAA substituiertem acac-Liganden verknüpft über eine CH2-Brücke konnte nicht hergestellt werden. Alle neutralen TAA-substituierten -diketonato Pt(II) und Ir(III) Komplexe zeigen keine Lumineszenz, außer dem Pt(II)-Komplex mit CH2-Gruppe. Dieser zeigt angeregte Zustände die in guter Übereinstimmung mit den Emissionslebenszeiten bei RT sind. Diese sind ähnlich denen der Referenz, was auf einen 3Pt(N^N)(O^O)- Zustand schließen lässt. Die Komplexe ohne CH2-Brücke zeigen zudem keine transiente Absorption was auf ein Charge-Transfer-Quenching aufgrund der direkten Verknüpfung zwischen Donor und Akzeptor zurückzuführen sein könnte. Der homoleptische fac Ir(N^N)3 Komplex weist weder Emission bei RT, noch transiente Absorption auf. Bei 77 K ist eine stark strukturierte Emission mit einer Abklingzeit von 14 s zu beobachten. Verglichen mit dem literaturbekannten Vergleichskomplex ist die Emission auf die Bevölkerung eines 3Ir(ppz)3-Zustandes zurückzuführen. Unsere Ergebnisse sind grundlegend für die Synthese weiterer Verbindungen mit stärkeren Akzeptoren, wie z. B. Naphthalenimid, um längerlebige ladungsgetrennte Zustände zu erhalten. Diese könnten Anwendung als Photosynthesiser in Solarzellen und anderen optoelektronischen Bauteilen finden. Zudem sind weiter Untersuchungen an LECs und OLEDs für die Carbazol-Komplexe noch immer von Interesse, um das Ausmaß der Triplett-Triplett-Annihilierung zu quantifizieren. / In the first part of this work we presented the synthesis and photophysical properties of a series of transition metal donor-acceptor Ir(III)complexes of the type [(C^N)2Ir(N^N)][PF6]. The Ir(III) was connected with hole conducting donor-moieties like carbazole (CZ) and triarylamine (TAA) linked via a methylene and ethylene bridge to the cyclometalating C^N ligands phenylpyrazole (ppz) and phenylpyridine (ppy). Bidentate N^N and P^P ligands like 2,2’-bipyridyl (bpy), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmp) and cis-1,2-bis(diphenylphosphino)ethylene (bdppe) were used as acceptor units. In order to analyse the influence of the electron density of the bpy ligand, TAA-complexes with acceptor- and donor-substituted bpy acceptor units were synthesised. Therefore, 4,4’-dinitro-2,2’-bipyridyl, 4,4’-dichloro-2,2’-bipyridyl, 4,4’-dimethoxy-2,2’-bipyridyl and 4,4’-dimethylamino-2,2’bipyridyl were used as neutral N^N ligands. In order to compare the photophysical properties, all reference compounds without hole conducting component were syntesised. All the carbazole compounds, except the bdppe complexes, exhibit emission and transient absorption properties similar to their reference compounds that make them interesting for OLED (organic light emitting device) applications. LEC (light emitting electrochemical cell) studies show a red shifted luminescence. The triarylamine compounds do not luminesce at RT but they exhibit an intense, blue-shifted and long-lived luminescence at 77 K in a rigid matrix. The transient absorption spectra differ strongly from that of their reference compounds. The spectra display characteristic features of the spectra of the isolated radical anions and cations supported by spectroelectrochemical measurements. Thus, it can be assumed that the transient states are charge separated (CS) states in which the positive charge is localised at the TAA donor units and the negative charge at the N^N acceptor units. The decays of the transient states are biexponentially what indicates the presence of two transient states, the 1CS and the 3CS state. To understand this behaviour the differently substituted bipyridyl-complexes were synthesised and analysed. Temperature dependent transient absorption measurements showed that all rate constants are indepentend of the temperature, except for the complex with OMe subsituents at the bpy ligand. The equilibrium constant K = k1 / k2 is nearly one for all complexes. For the OMe-compound it decreases with increasing temperature. Plotting the rate constants vs. the free energy differences (determined by cyclovoltammetry measurements) shows that all constants are decreasing with increasing donor strength of the bpy ligand. DFT calculations on the OMe-compound are already in work. In the second part of this work, neutral Ir(III) and Pt(II) complexes of the type [(O^O)Ir(N^N)2] and [(O^O)Pt(N^N)] were introduced. There, TTA was connected directly or via a CH2 bridge to acectylacetonate (acac = O^O) in order to probe the influence of the different kinds of connection on the photophysics of the complexes. As the bidentate N^N ligand 2,2’-bipyridyl (bpy) was chosen. All the corresponding reference compounds without triarylamine were obtained in order to compare with the TAA substituted analoga. Furthermore, the homoleptic fac Ir(N^N)3 complex with triarylamine connected via a methylene and ethylene bridge to phenylpyrazole as introduced in the first part of this work was synthesised. The synthesis of the Ir(III) compound with the TAA substituted acac ligand connected via the CH2 group was not successful. All the neutral triarylamine-substituted -diketonato Pt(II) and Ir(III) complexes do not luminesce at RT, except the Pt(II)-complex with CH2 bridge. This compound shows transient state characteristics that are in good agreement with the luminescence lifetimes at RT and that are similar to the reference compound, what suggests to a 3Pt(N^N)(O^O) state. The complexes without the CH2 bridging unit show no transient signals what may be caused by charge-transfer quenching due to the direct linkage between donor and acceptor unit. The homoleptic fac Ir(N^N)3 complex exhibits no emission at RT and no transient signals. At 77 K it shows a highly structured emission with 14 s lifetime. Compared to the literature-known reference compound this emission is caused by the population of a 3Ir(ppz)3 state. Our findings are important for designing complexes with stronger acceptor units (i.e. naphthaleneimide) for long CS states lifetimes to be used as photosynthesisers in solar cells and other optoelectronic devices. Besides, LEC and OLED studies on the carbazole complexes are still of interest to analyse the degree of triplet-triplet-annihiliation in these devices.
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Religious convictions in political discourse: moral and theological grounds for a public theology in a plural worldYaksic, Miguel January 2010 (has links)
Thesis advisor: Dominic Doyle / Moral, aesthetic, and religious pluralism has become a source of disagreement and friction in the modern world. Within the context of modernity and precipitated by the American and French revolutions, liberal democracy has aimed to organize the social and political life of societies in which their inhabitants sustain different, distant, and sometimes contradictory conceptions of the good life. Liberal secular principles have been the framework used to protect fundamental values such us freedom, equality, and mutual respect. In order to preserve the stability of a plural society, liberalism insists that moral and religious convictions must remain a private matter. Democracy and tolerance, it was argued, would be best preserved if religious convictions were removed from the public/political conversation. Yet the debate about the appropriate relationship between religion and politics regularly resurfaces among political and moral philosophers, social theorists, and theologians. / Thesis (STL) — Boston College, 2010. / Submitted to: Boston College. School of Theology and Ministry. / Discipline: Sacred Theology.
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Optimization of dense medium cyclone plant for the beneficiation of low grade iron ore with associated high proportion of near-density material at Sishen Iron Ore MineTom, Phakamile January 2016 (has links)
A research report submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in partial fulfilment of the requirements for the Degree of Master of Science in Engineering (Metallurgy and Materials Engineering) July 2015 / The research report is premised on three aspects which are critical in the heavy mineral beneficiation. These aspects are classified as (i) understanding the densimetric profile of the available ore body, (ii) understanding the properties of the heavy medium utilised at the plant to beneficiate the ore, and (iii) the automation and modelling of the processing plant in order to maximise plant efficiency.
Ore characterisation is mainly focused on understanding the densimetric profile of the ore body, in order to determine the probability of producing a saleable product as well as predicting the expected yields and quality. This is done to utilise the endowment entrusted upon the operating entity by the government and shareholders to treat the mineral resource to its full potential. Understanding of the beneficiation potential of the ore body will assist the mine planning and processing plant to optimise the product tons and quality. This will ensure the marketing plans are in accordance with the expected product as beneficiation will vary depending on the mining block reserves. The mining blocks have potential to produce varying product grades with different recoveries.
Ore characterisation was conducted on the GR80 mining block, low-grade stockpiles (i.e. C-grade ore reserves & Jig discard and dense medium separation (DMS) run-of-mine (ROM) material. The GR80 material was characterised as having low proportion of near-density material and would be easy to beneficiate as well as produce high volumes of high grade product. Furthermore, it was revealed that the 2014 DMS ROM had an increased proportion of low-density material; however this material was also had low proportion of near-density material.
The low-grade stockpiles was characterised by high proportion of near density material, which necessitate the beneficiation process to operate at high density in excess of 3.8 t/m3. Maintaining a higher operating density requires more dense medium which leads to viscosity problems and impact performance.
The characterisation of the FeSi medium was imperative to understand its behaviour and potential influence on beneficiation of low-grade stockpiles and mining blocks with elevated proportion of near-density material. As the proportion of near-density waste material increases in the run-of-mine (ROM), it is necessary to beneficiate the material at elevated operating
medium densities. However, when cyclones are operated at high densities, the negative influence of the medium viscosity becomes more apparent and thus influences the separation efficiency.
Heavy medium, ferrosilicon (FeSi) characterisation looked at identifying the effects of viscosity on the FeSi stability and whether there would be a need for a viscosity modifier. Thus, the importance of controlling the stability, viscosity, and density of the medium cannot be under-estimated and can very often override the improvements attainable through better designs of cyclones. Furthermore, the slurry mixture of the heavy medium utilised for the purpose of dense medium separation should be non-detrimental to the effectiveness of separation in the DMS Fine cyclone plant. Medium characterisation showed that removal of ultra-fines leads to unstable media as indicated by faster settling rates. This would result in medium segregation in the beneficiation cyclone thereby leading to unacceptable high density differential which will negatively impact the cut-point shift and cause high yield losses to waste.
The overall control of the metallurgical processes at Sishen’s Cyclone Plant is still done on manually and thus operation still varies from person-to-person and/or from shift-to-shift. This result in some of the process data and trends not being available online as well as being captured inaccurately. Furthermore, this negatively affects the traceability and reproducibility of the production metallurgical key performance indicators (KPI’s) as well as process stability and efficiency.
It has been demonstrated that real-time online measurements are crucial to maintaining processing plant stability and efficiency thereby ensuring that the final product grade and its value is not eroded. Modelling and automation of the key metallurgical parameters for the cyclone plant circuit was achieved by installation of appropriate instrumentation and interlocking to the programmable logic control (PLC). This allowed for the control of the correct medium sump level, cyclone inlet pressure, medium-to-ore ratio as well as online monitoring of density differential as “proxy” for medium rheological characteristics.
The benefit of modelling and simulation allows the virtual investigation and optimisation of the processing plant efficiency as well as analysis of the impact of varying ore characteristics, throughput variations and changing operating parameters. Therefore it is imperative that all cyclone operating modules are operated at the same efficiency which can be achieved by optimized process through proper automation and monitoring, thereby improving the total plant profitability.
Keywords: dense medium separation; densimetric profile; dynamic modelling; FeSi rheology; iron-ore beneficiation; process automation; process control.
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Feasible products and cost indicators for vapour-liquid equilibrium separation processesJobson, Megan Ruth January 1996 (has links)
A thesis submitted to the Faculty of Engineering, University of the Witwatersrand,
Johannesburg, South Africa in fulfilment of the requirements for the degree of
Doctor of Philosophy. / The aim of process synthesis is to select process equipment and interconnections in
order to achieve some performance goal, such as the composition of one or more
products, in an optimal manner. This work focuses on the synthesis and
optimization of vapour-liquid equilibrium (VLE) separation processes.
The regions of feasible products for a range of VLE separation processes (including
simple distillation, simple condensation and processes comprised of one or two flash
stages and mixing) are determined and analyzed. Binary and ternary systems, both
ideal and non-ideal, are considered. It is shows .at the products of VLE separation
processes are not inherently restricted; limitations in product composition are
therefore introduced by the choice of separation equipment. The products on the
boundary of the region of feasible products are often found to be associated with
infinite costs. Therefore costs and, product composition should he considered
simultaneously in process synthesis.
This work introduces a pair of variables which are proposed as cost indicators for
VLE separation processes. These variables, which are called "capacity variables",
pertain to distillation columns and a wide range of other VLE separation processes,
allowing their comparison. The variables incorporate both capital and energy costs
of a process and are thus related to total annual costs. They accommodate costs of
both boiling and condensing. They ate simple to calculate from the mass balance
equations. The capacity variables are analogous to mean residence time, which
serves as a cost indicator for processes invoi ving reaction.
The capacity variables are evaluated for a range of processes separatins binary and
ternary mixtures and a range of thermodynamic systems. The capacity variables
reflect the impact of the operating parameters, such as product specifications and
reflux ratio, on process costs. In distillation processes, the optimum reflux ratio is
found to be close to the beuristic value of 1.2 times the minimum reflux ratio. The
capacity variables are proposed as useful tools for the initial stages of process
synthesis. / Andrew Chakane 2018
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Nouveaux matériaux à conduction mixte protonique-électronique : Développement de membranes sélectives destinées à la séparation de l'hydrogène / Novel mixed protonic-electronic materials : Development of selective membranes devoted for hydrogen separationMao, Visot 05 December 2016 (has links)
La formulation de matériaux à conduction mixte protonique-électronique (MIEC-H+) performants constituerait une avancée majeure pour le développent d’applications liées au vecteur hydrogène. En particulier cette classe de matériaux constitue une alternative prometteuse aux membranes métalliques ou poreuses pour les dispositifs dédiés de la séparation de l’hydrogène. L’objectif de ce travail de thèse a ainsi été de développer, de caractériser des matériaux présentant des conductivités suffisantes pour l’application visée, de mettre en forme des membranes et d’évaluer leurs performances.La première approche a consisté développer des matériaux monophasiques par substitution d’oxydes conducteurs protoniques par un élément multivalent, Ba(Ce0.5Zr0.5)0.9-xPrxY0.1O3-δ). Parallèlement, nos travaux ont porté sur des composites céramique-céramique constitués d’une phase à conduction protonique et d’une phase à conduction électronique dans des conditions réductrices, xBaCe0.9Y0.1O3-δ-(1-x)Ce0.9Y0.1O2-δ et xBaZr0.9Y0.1O3-δ-(1-x)CeY0.1O2-δ.Les résultats les plus prometteurs en terme de conductivité (> 100 mS.cm-1 @ 600°C) ont été obtenus avec le composite de composition 20BaZr0.9Y0.1O3-δ-80Ce0.9Y0.1O2-δ qui présente une perméabilité à l’hydrogène (VALEUR) du même ordre de grandeur que les meilleures reportées dans la littérature. / The formulation of high-performance mixed protonic-electronic conductors (MPEC) presents a major advancement for the development of hydrogen-linked application. In particular, this class of materials constitute a promising alternative to the metallic or porous membranes for devices devoted for separation of hydrogen. Thus, objective of this thesis work is to develop, characterize materials presenting sufficient conductivities for the targeted applications, to fabricate the membrane and to evaluate their performances.The first approach consisted of developing single-phase materials by substitution of proton-conducting oxides by a multivalent element, Ba(Ce0.5Zr0.5)0.9-xPrxY0.1O3-δ. In parallel, our works focused on the ceramic-ceramic composites which were consisted of a proton-conducting phase and an electron-conducting phase in reducing conditions, xBaCe0.9Y0.1O3-δ-(1-x)Ce0.9Y0.1O2-δ et xBaZr0.9Y0.1O3-δ-(1-x)CeY0.1O2-δ.The most promising results in terms of conductivity (> 100 mS.cm-1 @ 600°C) was obtained with the composite of composition 20BaZr0.9Y0.1O3-δ-80CeY0.1O2-δ which presented hydrogen permeability in the same order of magnitude as the best values reported in the literature.
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Investigation and control of three-dimensional separation/stall in compressorsSun, Jinjing 29 January 2018 (has links)
Pas de résumé / As one of the key components in the modern propulsion system, compressor plays an important role on the performance of the aero-engine. Flow near the endwall in the compressor is complex and corner separation which generates at the corner region by the blade suction surface and the endwall is an inherent flow structure in the blade passage. As a reduction of the compressor performance can be caused by the corner separation especially at off-design and multi-stage conditions. Understanding the mechanism and also control of the corner separation is an effective approach to enhance the compressor stability. Mechanism and control methods of the corner separation in the cascade passage have been investigated in this thesis, following contents are included: l. Simulation by the RANS methods on a highly-loaded PVD cascade has been conducted. The numerical method used is verified by the comparison with the experiment. The topology analysis, overall performance and the flow characteristics of the corner separation are analyzed. The effects of some aerodynamic parameters such as the solidity, aspect ratio and blade fillet on the corner separation have also been studied. 2. The control effects of one active control method by the boundary layer suction and two passive control methods by the slot at the root of the blade and the hub clearance on the corner separation in PVD cascade are studied and compared systematically. The slot configuration on the blade combined under the influence of the aerodynamic parameters have also been conducted in order to know the cascade performance by the aerodynamic parameters under the introduction of the control method. 3. Optimization of the slot configuration at 4° incidence angle is conducted on the NACA65 cascade of LMFA in Lyon. The optimized slotted cascade is verified by the experiment at three incidence angle. 4. DDES method based on the SST k - ω model is used to simulate the optimized NACA65 slotted cascade. The turbulent characteristics in the corner separation and slot jet flow are analyzed, such as the turbulent anisotropy and the velocity spectra. 5. The study of the slot configuration on the corner separation is carried out on a realistic fan stator with high loading and high Mach number. The feasibility and effectiveness of this passive control method in the practical engineering are verified.
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Convex geometry-based blind separation of quasi-stationary sources / CUHK electronic theses & dissertations collectionJanuary 2014 (has links)
Fu, Xiao. / Thesis Ph.D. Chinese University of Hong Kong 2014. / Includes bibliographical references (leaves 145-154). / Abstracts also in Chinese. / Title from PDF title page (viewed on 15, September, 2016).
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The synthesis of Pd-Ag composite membranes for H2 separation using electroless plating methodBhandari, Rajkumar ms 14 January 2010 (has links)
One of the key elements to the success of Pd-Ag membrane based reactor for the H2 production is the synthesis of thin and highly selective membranes using the electroless plating method. This work describes the effect of electroless plating conditions on the obtained Pd and Ag deposits properties (morphology, compactness, phase structure, compositional homogeneity and adhesion) important from synthesis of thin and H2 selective membrane viewpoint. Both sequential and co-deposition deposition methods were investigated. The conventional Pd and Ag plating conditions (NH3+EDTA based bath) produced dendritic and non-uniform sequential (multi layer) deposits, not suitable for synthesizing the thin and H2 selective Pd-Ag membranes. Ag under the conventional plating conditions deposited at high overpotential resulting in the dendritic and non-uniform sequential deposits. The modified Ag plating conditions eliminated Ag deposition at high overpotential and the sequential deposits obtained were non-dendritic and uniform. Thin (< 10 µm thick) and H2 selective Pd-Ag membranes were successfully synthesized using the modified Ag plating conditions. The membranes were then successfully annealed at 550 oC. After the annealing step, the membranes showed activation energy for the H2 permeation (4.3-11.5 kJ/mole) lower than that of the pure Pd membrane (12-16.4 kJ/mole) meaning that the Pd-Ag membranes were more effective for the H2 separation at lower temperatures than the pure Pd membrane. A Pd-Ag (20 wt%) membrane showed H2 permeance higher by a factor of 2.47 at 250 oC than the pure Pd foil. The Pd-Ag membranes also showed decline in the H2/He selectivity on exposure to the annealing and H2 permeation (300-500 oC) study conditions. The Pd-Ag co-deposits obtained (using NH3+EDTA bath) were dendritic, inhomogeneous with poor substrate adhesion, therefore not suitable for the membrane synthesis. The co-deposits were bi-metallic and required the annealing step to form the Pd-Ag alloy. There existed a large difference in the deposition potentials (600 to 650 mV) of Pd and Ag. The Ag deposition was severely controlled by its mass transfer in the solution resulting in the dendritic and inhomogeneous deposits. Among the different complexing agents investigated, KCl showed the least difference between the Pd and Ag deposition potentials. The co-deposits obtained using the KCl bath were non-dendritic, homogeneous and were Pd-Ag alloy therefore required no annealing step. Finally, the multi step plating, annealing and polishing approach was used to avoid the decline in the selectivity of the sequentially prepared Pd-Ag membranes. The membranes prepared by the plating, annealing and polishing approach showed very high selectivity (H2/He) and no decline in the selectivity was observed between 300-450 oC for the total exposure time > 550 h (> 200 h at 450 oC).
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Supported Liquid Metal Membranes for Hydrogen SeparationYen, Pei-Shan 25 April 2016 (has links)
Hydrogen (H2) and fuel cells applications are central to the realization of a global hydrogen economy. In this scenario, H2 may be produced from renewable biofuels via steam reforming and by solar powered water electrolysis. The purification required for fuel cell grade H2, whether in tandem or in situ within a catalytic reformer operating at 500 oC or above, would be greatly facilitated by the availability a cheaper and more robust option to palladium (Pd) dense metal membrane, currently the leading candidate. Here we describe our results on the feasibility of a completely novel membrane for hydrogen separation: Sandwiched Liquid Metal Membrane, or SLiMM, comprising of a low-melting, non-precious metal (e.g., Sn, In, Ga) film held between two porous substrates. Gallium was selected for this feasibility study to prove of the concept of SLiMM. It is molten at essentially room temperature, is non-toxic, and is much cheaper and more abundant than Pd. Our experimental and theoretical results indicate that the Ga SLiMM at 500 oC has a permeability 35 times higher than Pd, and substantially exceeds the 2015 DOE target for dense metal membranes. For developing a fundamental understanding of the thermodynamics and transport in liquid metals, a Pauling Bond Valence-Modified Morse Potential (PBV-MMP) model was developed. Based on little input, the PBV-MPP model accurately predicts liquid metal self-diffusion, viscosity, surface tension, as well as thermodynamic and energetic properties of hydrogen solution and diffusion in a liquid metal such as heat of dissociative adsorption, heat of solution, and activation energy of diffusion. The concept of SLiMM proved here opens up avenues for development practical H2 membranes, For this, improving the physical stability of the membrane is a key goal. Consequently, a thermodynamic theory was developed to better understand the change in liquid metal surface tension and contact angle as a function of temperature, pressure and gas-phase composition.
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