Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2009. / The study concerns the use of the electrospinning technique for the formation of cellulose acetate hollow nanofibers. These hollow fibers are used to manufacture hollow fiber membranes. Important properties that should be inherent to these hollow-nanofibers include excellent permeability and separation characteristics, and long useful life. They have potential applications in filtration, reverse osmosis, and the separation of liquids and gases. It is apparent from the available literature on electrospinning and co-electrospinning that the diameter and the morphology of the resulting fibers are significantly influenced by variations in the system and process parameters, which include the solution concentration, solvent volatility, solution viscosity, surface tension and the conductivity of the spinning solution. The materials used include cellulose acetate (CA) (concentration = 11~14 wt %), (feed rate = 1~3 ml/h), acetone:dioxane (2:1) and mineral oil (feed rate = 0.5~1 ml/h) with core and shell linear velocity of 2 and 0.7 mm/min respectively. These materials were used as received without further purification. The co-electrospinning setup used comprised a compound spinneret, consisting of two concentric small-diameter capillary tubes/needles, one located inside another (core-shell/co-axial design). The internal and external diameters of the inside and outside needles were 0.3 and 1.2 mm respectively (0.3 mm shell/core gap space). The liquids CA (shell) and mineral oil (core) are pumped to the coaxial needle by a syringe pump, forming a compound droplet at the tip of the needle. A high voltage source is used to apply a potential of several kilovolts over the electrospinning distance. One electrode is placed into the spinning solution and the other oppositely charged (or neutral) electrode attached to a conductive collector. If the charge build up reaches approximately 15 kV the charged compound droplet, (poorly conductive polymer solution) deforms into a conical structure called a Taylor cone. On further increasing, the charge at the Taylor cone to some critical value (unique to each polymer system) the surface tension of the compound Taylor cone is broken and a core-shell jet of polymer solution ejects from the apex of the Taylor cone. This jet is linear over a small distance, and then deviates in a course of violent whipping from bending instabilities brought about by repulsive charges existing along the jet length. The core-shell jet is stretched and solvent is evaporated and expelled, resulting in the thinning and alignment of the fiber. Ultimately dry (most solvent having been removed) submicron fibers are collected in alignment form in a simple collector design (water bath). The shell to core solution flow rate ratio was chosen according to the parameter response of shell-core diameter of the resulting fibers in order to achieve an optimal hollow structure after removal of the mineral oil core. The mineral oil of the dry collected core-shell fibers is removed by immersion in octane. The aforementioned response is determined by measurement of core-shell diameters using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The obtained results showed that the ability of the spinning solution to be electrospun was directly dependent on its concentration and the feed rate of the spinning solution and also parameters such as the spinning distance and type of solvents used. The preferable polymer solution concentration is 14 wt %, shell feed rate of 3 ml/hr, core feed rate of 0.5 ml/hr (2 and 0.7 mm/s core and shell linear velocity respectively), applied voltage of 15 KV, spinning distance of 8 cm and coaxial spinnerets having internal diameters of 0.3 mm and 1.2 mm core and shell needles respectively (0.3 mm shell/core gap space) have been found to make uniform cellulose acetate hollow fibers with an average inside and outside diameter of approximately 495 and 1266 nm, respectively.

Mixed matrix membranes offer an attractive route to the development of high performance and efficiency membranes required for demanding gas separations. Such membranes combine the advantageous processing characteristics of polymers with the excellent separation productivity and efficiency of molecular sieving materials. This research explores the development of mixed matrix membranes, namely in the form of asymmetric hollow fiber membranes using zeolites as the molecular sieving phase and commercially available high performance polymers as the continuous matrix. Lack of adhesion between the typically hydrophobic polymer and the hydrophilic native zeolite surface is a major hurdle impeding the development of mixed matrix membranes. Silane coupling agents have been used successfully to graft polymer chains to the surface of the zeolite to increase compatibility with the bulk polymer in dense films. However, transitioning from a dense film to an asymmetric structure typically involves significant processing changes, the most important among them being the use of phase separation to form the asymmetric porous structure. During the phase separation, it is believed that hydrophilic sieves can act as nucleating agents for the hydrophilic polymer lean phase. Such nucleation tendencies are believed to lead to the formation of gaps between the polymer and sieve resulting in poor mixed matrix performance. This research focuses on defining procedures and parameters to form successful mixed matrix hollow fiber membranes. The first part of this dissertation describes dope mixing procedures and unsuccessful results obtained using a silane coupling agent to enhance polymer-zeolite adhesion. The next section follows the development of a highly successful surface modification technique, discovered by the author, employing the use of a Grignard reagent. As a test case, two zeolites of different silicon-to-aluminum ratios are successfully modified and used to develop mixed matrix membranes with greatly increased gas separation efficiencies. The broad applicability of the surface treatment is also demonstrated by the successful incorporation of the modified zeolites in a second polymer matrix. The final section of the work describes the novel occurrence of large defects (macrovoids) caused by the presence of large zeolite particles proposing a particle size effect in the formation of such defects.

Compared to the conventional amine adsorption process to separate CO₂ from natural gas, the membrane separation technology has exhibited advantages in easy operation and lower capital cost. However, the high CO₂ partial pressure in natural gas can plasticize the membranes, which can lead to the loss of CH₄ and low CO₂/CH₄ separation efficiency. Crosslinking of polymer membranes have been proven effective to increase the CO₂ induced plasticization resistance by controlling the degree of swelling and segmental chain mobility in the polymer. This thesis focuses on extending the success of crosslinking to more productive asymmetric hollow fibers. In this work, the productivity of asymmetric hollow fibers was optimized by reducing the effective selective skin layer thickness. Thermal crosslinking and catalyst assisted crosslinking were performed on the defect-free thin skin hollow fibers to stabilize the fibers against plasticization. The natural gas separation performance of hollow fibers was evaluated by feeding CO₂/CH₄ gas mixture with high CO₂ content and pressure.

Post-combustion carbon capture, wherein the CO2 produced as a result of coal combustion is trapped at the power plant exhaust, is seen as a bridging technology to reduce CO2 emissions and combat climate change. This capture process will however impose a parasitic load on the power plant and technologies need to be developed to minimize this energy penalty. This research focuses on a technology which uses solid sorbents fashioned into a hollow fiber form that allows water-moderated thermal cycling as a means of trapping CO2 from flue gas. While hollow fiber technology has intrinsic advantages over competing liquid amine and packed bed technologies, the materials used to fabricate hollow fibers and the fabrication process itself need to be optimized in order to result in competitive, robust hollow fiber sorbents. This dissertation focuses on the material selection process for each component of the hollow fiber platform and discusses ways to optimize the fiber and barrier layer formation. Different materials were evaluated to function as the solid sorbent, the matrix polymer and the barrier layer; and eventually their performance was measured against past work in this area.

Tato diplomová práce se zabývá výrobou ultratenkých keramických dutých vláken pomocí metody povlakování namáčením. Příprava keramických dutých vláken je v současnosti limitována rozměrem vnějšího a vnitřního průměru. Aplikace metody povlakování namáčením pro přípravu ultratenkých dutých je nový a technologicky náročný proces vyžadující volbu vhodné šablony a zároveň zvládnutí kontroly parametrů povlakování. Základními zvolenými materiály s vysokým aplikačním potenciálem jsou hydroxyapatit a oxid titaničitý. Samonosná dutá vlákna s tloušťkou stěny pod 1 m byla úspěšně připravena z obou materiálů. Dále byl také popsán proces povlakování namáčením obětovaných šablon. Tato metoda je unikátní, protože umožňuje produkci ultratenkých keramických dutých vláken s vnitřním průměrem pod 100 m a tloušťkou stěny pod 1 m.

Disertační práce je zaměřena na kovové a polymerní výměníky tepla. Hlavním předmětem zkoumání je optimalizace teplosměnných ploch za účelem zvýšení účinnosti výměníku tepla. Tyto cíle byly dosaženy experimentálně a numericky pomocí modelování v ANSYS. Na základě dosažených výsledků byla rozpracována technologie křížového navíjení polymerních výměníků z dutých vláken. Experimentální zařízení původně určené pro navíjení tlakových nádrží bylo modifikované pro automatizovanou výrobu polymerních výměníků z dutých vláken, ježto může být použita při jejich masové výrobě. Tato práce se také zabývala výměníky tepla pro klimatizační systémy. Byly zkoumány možnosti využití polymerních výměníků z dutých vláken v těchto systémech. Mimo jiné byla provedena studie vlivu cyklického tepelného zatížení standardního kovového žebrovaného tepelného výměníku.

This master’s thesis deals with the design and manufacture of a heat exchanger with polymeric hollow fibers for a Formula Student vehicle. The work can be divided into three parts. The first part contains a review of heat transfer and heat exchangers, the second part deals with polymeric fiber heat exchangers design and manufacture of of polymeric hollow fibers heat exchanger with a heat exchanger for a Formula Student vehicle. The last part deals with the comparison of polymeric hollow fibers heat exchanger with the original aluminum heat exchanger and the evaluation of the measurement results.

The diploma thesis is devoted to the separation of a gasseous pollutant (CO2) from a gas mixture using an experimental technology device - membrane contactor. The theoretical part is mostly focused on the recent progress in the field of membrane contactors. The theoretical part also contains theory of absorption, which is needed to understand the subject properly. The experimental part focuses on the construction of the experimental device. The efficiency of the device in absorption of carbon dioxide to an aqua solution of sodium hydroxide was tested. At the end, experimental data are discussed.

The global market for membrane separation technologies is forecast to reach $16 billion by the year 2017 due to wide adoption of the membrane technology across various end-use markets. With the growth in demand for high quality products, stringent regulations, environmental concerns, and exhausting natural resources, membrane separation technologies are forecast to witness significant growth over the long term (Global Industry Analysts Inc., 2011). The future of membrane technology promises to be equally exciting as new membrane materials, processes and innovations make their way to the marketplace. The current trend in membrane gas separation industry is, however, to develop robust membranes, which exhibit superior separation performance, and are reliable and durable for particular applications. Process simulation allows the investigation of operating and design variables in the process, and in new process configurations. An optimal operating condition and/or process configuration could possibly yield a better separation performance as well as cost savings. Moreover, with the development of new process concepts, new membrane applications will emerge. The thesis addresses developing models that can be used to help in the design and operation of CO2 capture processes. A mathematical model for the dynamic performance of gas separation with high flux, asymmetric hollow fiber membranes was developed considering the permeate pressure build-up inside the fiber bore and cross flow pattern with respect to the membrane skin. The solution technique is advantageous since it requires minimal computational effort and provides improved solution stability. The model predictions and the robustness of the numerical technique were validated with experimental data for several membrane systems with different flow configurations. The model and solution technique were applied to investigate the performance of several membrane module configurations for air separation and methane recovery from biogas (landfill gas or digester gas). Recycle ratio plays a crucial role, and optimum recycle ratios vital for the retentate recycle to permeate and permeate recycle to feed operation were found. From the concept of two recycle operations, complexities involved in the design and operation of continuous membrane column were simplified. Membrane permselectivity required for a targeted separation to produce pipeline quality natural gas by methane-selective or nitrogen-selective membranes was calculated. The study demonstrates that the new solution technique can conveniently handle the high-flux hollow fiber membrane problems with different module configurations. A section of the study was aimed at rectifying some commonly believed perceptions about pressure build-up in hollow fiber membranes. It is a general intuition that operating at higher pressures permeates more gases, and therefore sometimes the membrane module is tested or characterized at lower pressures to save gas consumption. It is also perceived that higher pressure build-up occurs at higher feed pressures, and membrane performance deteriorates at higher feed pressures. The apparent and intrinsic permeances of H2 and N2 for asymmetric cellulose acetate-based hollow fiber membranes were evaluated from pure gas permeation experiments and numerical analysis, respectively. It was shown that though the pressure build-up increases as feed pressure increases, the effect of pressure build-up on membrane performance is actually minimized at higher feed pressures. Membrane performs close to its actual separation properties if it is operated at high feed pressures, under which conditions the effect of pressure build-up on the membrane performance is minimized. The pressure build-up effect was further investigated by calculating the average loss and percentage loss in the driving force due to pressure build-up, and it was found that percentage loss in driving force is less at high feed pressures than that at low feed pressures. It is true that unsteady state cyclic permeation process can potentially compete with the most selective polymers available to date, both in terms selectivity and productivity. A novel process mode of gas separation by means of cyclic pressure-vacuum swings for feed pressurization and permeate evacuation using a single pump was evaluated for CO2 separation from flue gas. Unlike transient permeation processes reported in the literature which were based on the differences in sorption uptake rates or desorption falloff rates, this process was based on the selective permeability of the membrane for separations. The process was analyzed to elucidate the working principle, and a parametric study was carried out to evaluate the effects of design and operating parameters on the separation performance. It was shown that improved separation efficiency (i.e., product purity and throughput) better than that of conventional steady-state permeation could be obtained by means of pressure-vacuum swing permeation. The effectiveness of membrane processes and feasibility of hybrid processes combining membrane permeation and conventional amine absorption process were investigated for post-combustion CO2 capture. Traditional MEA process uses a substantial amount of energy at the stripper reboiler when CO2 concentration increases. Several single stage and multi-stage membrane process configurations were simulated for a target design specification aiming at possible application in enhanced oil recovery. It was shown that membrane processes offer the lowest energy penalty for post-combustion CO2 capture and likely to expand as more and more CO2 selective membranes are developed. Membrane processes can save up to 20~45% energy compared to the stand-alone MEA capture processes. A comparison of energy perspective for the CO2 capture processes studied was drawn, and it was shown that the energy requirements of the hybrid processes are less than conventional MEA processes. The total energy penalty of the hybrid processes decreases as more and more CO2 is removed by the membranes.

The global market for membrane separation technologies is forecast to reach $16 billion by the year 2017 due to wide adoption of the membrane technology across various end-use markets. With the growth in demand for high quality products, stringent regulations, environmental concerns, and exhausting natural resources, membrane separation technologies are forecast to witness significant growth over the long term (Global Industry Analysts Inc., 2011). The future of membrane technology promises to be equally exciting as new membrane materials, processes and innovations make their way to the marketplace. The current trend in membrane gas separation industry is, however, to develop robust membranes, which exhibit superior separation performance, and are reliable and durable for particular applications. Process simulation allows the investigation of operating and design variables in the process, and in new process configurations. An optimal operating condition and/or process configuration could possibly yield a better separation performance as well as cost savings. Moreover, with the development of new process concepts, new membrane applications will emerge. The thesis addresses developing models that can be used to help in the design and operation of CO2 capture processes. A mathematical model for the dynamic performance of gas separation with high flux, asymmetric hollow fiber membranes was developed considering the permeate pressure build-up inside the fiber bore and cross flow pattern with respect to the membrane skin. The solution technique is advantageous since it requires minimal computational effort and provides improved solution stability. The model predictions and the robustness of the numerical technique were validated with experimental data for several membrane systems with different flow configurations. The model and solution technique were applied to investigate the performance of several membrane module configurations for air separation and methane recovery from biogas (landfill gas or digester gas). Recycle ratio plays a crucial role, and optimum recycle ratios vital for the retentate recycle to permeate and permeate recycle to feed operation were found. From the concept of two recycle operations, complexities involved in the design and operation of continuous membrane column were simplified. Membrane permselectivity required for a targeted separation to produce pipeline quality natural gas by methane-selective or nitrogen-selective membranes was calculated. The study demonstrates that the new solution technique can conveniently handle the high-flux hollow fiber membrane problems with different module configurations. A section of the study was aimed at rectifying some commonly believed perceptions about pressure build-up in hollow fiber membranes. It is a general intuition that operating at higher pressures permeates more gases, and therefore sometimes the membrane module is tested or characterized at lower pressures to save gas consumption. It is also perceived that higher pressure build-up occurs at higher feed pressures, and membrane performance deteriorates at higher feed pressures. The apparent and intrinsic permeances of H2 and N2 for asymmetric cellulose acetate-based hollow fiber membranes were evaluated from pure gas permeation experiments and numerical analysis, respectively. It was shown that though the pressure build-up increases as feed pressure increases, the effect of pressure build-up on membrane performance is actually minimized at higher feed pressures. Membrane performs close to its actual separation properties if it is operated at high feed pressures, under which conditions the effect of pressure build-up on the membrane performance is minimized. The pressure build-up effect was further investigated by calculating the average loss and percentage loss in the driving force due to pressure build-up, and it was found that percentage loss in driving force is less at high feed pressures than that at low feed pressures. It is true that unsteady state cyclic permeation process can potentially compete with the most selective polymers available to date, both in terms selectivity and productivity. A novel process mode of gas separation by means of cyclic pressure-vacuum swings for feed pressurization and permeate evacuation using a single pump was evaluated for CO2 separation from flue gas. Unlike transient permeation processes reported in the literature which were based on the differences in sorption uptake rates or desorption falloff rates, this process was based on the selective permeability of the membrane for separations. The process was analyzed to elucidate the working principle, and a parametric study was carried out to evaluate the effects of design and operating parameters on the separation performance. It was shown that improved separation efficiency (i.e., product purity and throughput) better than that of conventional steady-state permeation could be obtained by means of pressure-vacuum swing permeation. The effectiveness of membrane processes and feasibility of hybrid processes combining membrane permeation and conventional amine absorption process were investigated for post-combustion CO2 capture. Traditional MEA process uses a substantial amount of energy at the stripper reboiler when CO2 concentration increases. Several single stage and multi-stage membrane process configurations were simulated for a target design specification aiming at possible application in enhanced oil recovery. It was shown that membrane processes offer the lowest energy penalty for post-combustion CO2 capture and likely to expand as more and more CO2 selective membranes are developed. Membrane processes can save up to 20~45% energy compared to the stand-alone MEA capture processes. A comparison of energy perspective for the CO2 capture processes studied was drawn, and it was shown that the energy requirements of the hybrid processes are less than conventional MEA processes. The total energy penalty of the hybrid processes decreases as more and more CO2 is removed by the membranes.