Thesis (Ph.D.)--Auburn University, 2007. / Abstract. Vita. Includes bibliographic references (ℓ. 280-297)

Thesis (Ph. D.)--Ohio State University, 2005. / Available online via OhioLINK's ETD Center; full text release delayed at author's request until 2008 Dec 31

Direct capture of CO2 from ambient air is a developing technology, which is capable of removing CO2 directly from the atmosphere. Moreover, this technology is independent from sources of CO2 emissions. Hence, it can be set up at locations where pure stream of CO2 is needed such as in enhanced oil recovery. In this research, the performance of pelletized and natural limestone for CO2 capture from air in a fixed bed is studied. To compare the performance of sorbents for air capture, the effects of particle type (natural limestone and pelletized limestone), particle size (250-425 µm and 425-600 µm), gas flowrate (0.5 L/min and 1 L/min), and relative humidity, on the breakthrough time, breakthrough shape, and the global reaction rate are examined. Moreover, carbonation decay of sorbents over series of capture and regeneration cycles is studied. If the inlet stream (air) is humidified at 50% relative humidity, but the lime sorbents are not pre-hydrated, an axially non-uniform carbonated bed results. This phenomenon is due to the partial carbonation of sorbents at the first layers of the bed. While there is a competition between CO2 and water to react with CaO, partial carbonation reaction on the surface of the sorbents not only prevents further hydration, but also decreases the reaction rate at the surface. However, in comparison with a dry system where relative humidity was negligible and sorbents were not pre-hydrated, the observed carbonation conversion was higher. The best results were seen from experiments with pre-hydrated sorbents and humidified inlet stream. The smaller sorbent particles had a better performance (sharper breakthrough curve and longer breakthrough time) due to their greater surface area. A gas-solid reaction model was fitted to the breakthrough curves. Since at the beginning of carbonation there is no resistance of the product layer, it can be assumed that the process is reaction controlled. While after formation of the product layer (CaCO3), it becomes diffusion controlled. Results from fitted data also confirmed these conclusions. Moreover, each of sorbent went through 9 cycles and after each cycle the carbonation conversion of the sorbents was measured by TGA and the surface area by BET.

The use of collection systems for magnetic sorbents such as Magnetic Activated Carbon are discussed in order to gauge their efficacy in marine environments. Two collectors were built and tested, one which utilized a radial orientation of magnets and another with axially placed magnets. The two systems underwent a series of test with differing linear velocities and angular velocities. From the results, the axial system outperformed its radial counterpart, being most effective with a relatively high concentration of discs placed in series. The medium concentration, however, proved increasingly effective with higher velocities, meaning an optimization concentration exists for this design. The radial system was tested with high and low concentrations of small and large magnets, respectively. The larger magnets, although providing less concentration points in the alternating array, proved more effective for the collection of MAC. From these tests several new innovations were suggested, including belt tensioners, add on mechanisms, and a hybridized design in order to fully optimize the collection of MAC.

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As concerns mount about the rise in atmospheric CO₂ concentrations, many different routes to reduce CO₂ emissions have been proposed. Of these, post-combustion CO₂ capture from coal-fired power stations is often the most controversial, as the CO₂ capture system will remove generating capacity from the grid whereas many of the other solutions involve increasing the generating capacity of the grid with low CO₂-emission plants. Despite this, coal-fired power stations represent a major point source for CO₂ emissions, and if a consensus is reached on the need to reduce CO₂ emissions, a low-cost method for capturing and storing the CO₂ released by these power plants needs to be developed. The overarching goal of this research is to design and develop a novel hollow fiber sorbent system for post-combustion CO₂ capture. To achieve this goal, three objectives were developed to guide this research: i) develop a conceptual framework for hollow fiber sorbents that focuses on the energetic requirements of the system, ii) demonstrate that hollow fiber sorbents can be created, and a defect-free lumen layer can be made, iii) perform proof-of-concept CO₂ sorption experiments to confirm the validity of this approach to CO₂ capture. Each of these objectives is addressed in the body of this dissertation. Work on the first objective showed that fiber sorbents can combine the energetic advantages of a physi-/chemi-sorption process utilizing a solid sorbent while mitigating the process deficiencies associated with using solid sorbents in a typical packed bed. All CO₂ capture technologies--including fiber sorbents--were shown to be highly parasitic to a host power plant in the absence of effective heat integration. Fiber sorbents have the unique advantage that heat integration is enabled most effectively by the hollow fiber morphology: the CO₂-sorbing fibers can behave as "adsorbing heat exchangers." A dry-jet, wet-quench based hollow fiber spinning process was utilized to spin fibers that were 75wt% solid sorbent (zeolite 13X) and 25wt% support polymer (cellulose acetate). The spinning process was consistent and repeatable, allowing for production of large quantities of fibers. The fibers were successfully post-treated with an emulsion-based polymer (polyvinylidene chloride) to create a defect-free lumen side coating that was an excellent barrier to both water and gas permeation. A film study was conducted to elucidate the dominant factors in the formation of a defect-free film, and these factors were used for the creation of defect-free lumen layers. The work discussed in this thesis shows that the second objective of this work was definitively achieved. For the third objective, sorption experiments conducted on the fiber sorbents indicated that the fiber sorbents CO₂ uptake is simply a weighted average of the support material CO₂ uptake and the solid sorbent uptake. Furthermore, kinetic experiments indicate that CO₂ access to the sorbents is not occluded noticeably by the polymer matrix. Using the fiber sorbents in a simulated rapid thermal swing adsorption cycle provided evidence for the fiber sorbents ability to capture the sorption enthalpy released by the CO₂-13X interaction. Finally, a slightly more-pure CO₂ product was able to be generated from the fiber sorbents via a thermal swing/inert purge process.

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.

<p>The main objectives of this study were to investigate (i) anovel wetland treatment technology and (ii) selected bed filtermedia for the removal of contaminants from landfill leachate. Areview of the literature concerning experiences of the use ofconstructed wetlands (CW) for the removal of nitrogen fromlandfill leachate, showed that at least three groups oftreatment systems are in practice: sub-surface flow wetlands,hybrid systems (a combination of vertical and horizontal flowwetlands) and, compact constructed wetland (CCW). Most of thesetypeswere generally effective in reducing nitrogen (N,<i>e.g.</i>NH₄-N, dominant N species in leachate) down toeffluent concentrations of about 10 mg L^-1. Unfortunately, very little evidence ofresponsible mechanisms for the removal of N was presented,although some data indicated denitrification. The treatmentperformance of a compact constructed wetland (CCW) applied atthe Tveta Landfill, Södertälje, Sweden, wasevaluated. Chemically purified leachate and untreated leachatewere applied in periods of 7 day submergence and 7 day drainageto different sections of the CCW. The removal efficiency variedbetween 40 and 82%, and a mass removal rate of up to 5.1 g m²d^-1was achieved. The chemical pre-treatment had adecisive role for the highest removal efficiencies obtained andit was unclear whether that treatment enhanced the efficiencybecause of lower toxicity and/or content of fewer competingcations. The possible combination of bed filter media and CCWas an ecotechnological treatment method for landfill leachatewas investigated by bench-scale laboratory column experiments.Reactive filter media (sorbents) was selected from their knownor suggested capacities for removal of heavy metals, nitrogenand phosphorus. Quartz sand or natural sand from an esker wasused as reference medium. Peat was used as an additionalcomponent in mixtures with the reactive media Polonite^®(product from the bedrock opoka) and blastfurnace slag (BFS). A small column study also involved zeolite.Phosphorus was efficiently removed by Polonite^®and NH₄-N to some extent. Concerning metal removal, thebest performance was found as well for Polonite^®, especially for Mn, Fe, Zn and Cu. The BFSshowed good removal efficiency for Cu, Ni and Mo. The removalof different elements was suggested to be a combination ofseveral factors,<i>e.g.</i>precipitation, ion exchange and adsorption. Priorto full-scale application of reactive filters at a landfillsite, matrix selection, filter design and operationalprocedures must be developed.</p><p><b>Keywords:</b>Blast furnace slag; Compact constructedwetland; Metals; Nitrogen; Polonite; Sorbents</p>

The effect of the physical state and chemical composition on molecular interactions has been studied for a number of chemically modified adsorbents. During the course of the study a reaction scheme was put together for the synthesis of a particular substituted crown ether. The synthesized allyl-benzo-15crown-5, which is not reported in the literature to date, was silylated and immobilized on a silica surface. The bonded phase was characterized by UV spectroscopy and by chromatography under both "normal" and "reverse" phase conditions. UV spectroscopy was also used to elucidate the physical state of several other phenyl alkyl bonded phases. Chromatographically, the bonded crown ether phase was found to be more polar than a C₈ stationary phase. A comparison of the selectivity of the two phases revealed that the former has a better selectivity towards a homologous series of alkyl benzenes under different reverse phase conditions. The selectivity of the crown ether phase was found to be dependent on the nature of the organic modifier in the mobile phase. This dependence was considered to be added evidence for the universality of the dynamic solvated stationary phase model. Both normal and reverse phase chromatographic conditions indicated an acid-base type of interaction between the crown ether and a number of substituted phenols. This was reflected in an increase in the retention of these probes as a function of their increasing acidity. A dramatic temperature effect observed on the crown ether stationary phase under aqueous THF mobile phase, but not under aqueous MeOH, was attributed to a temperature and/or solvent-induced phase change. A hysteresis effect, also seen only with aqueous THF, indicated that the crown ether phase undergoes a solvent-assisted conformational change. Further evidences for such a change was found spectroscopically in the abrupt break in the UV absorbance of these molecules as a function of temperature, as well as the irreversibility of the absorbance of the n- π* band on cooling. UV spectroscopy of bonded phenyl alkyls showed that there are about two monolayers of water molecule strongly adsorbed to the surface and totally impermeable to lypophilic species. Evidence for the existence of a solvated crystal, or liquid crystal, like clusters was rationalized with a cooperative sorption effect which may be dependent on the reaction conditions during immobilization. Despite a significant increase in the liquid character observed as the chain length is increased to 4-7 methylene groups, the bonded clusters still appear to preserve a fairly ordered environment. The physical state of the immobilized species was found to change with the experimental conditions and the change was reflected on the selectivity of the system.