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- Creators: Arizona State University
- Creators: Deng, Shuguang
- Member of: ASU Electronic Theses and Dissertations
- Status: Published
Description
Emergent environmental issues, ever-shrinking petroleum reserves, and rising fossil fuel costs continue to spur interest in the development of sustainable biofuels from renewable feed-stocks. Meanwhile, however, the development and viability of biofuel fermentations remain limited by numerous factors such as feedback inhibition and inefficient and generally energy intensive product recovery processes. To circumvent both feedback inhibition and recovery issues, researchers have turned their attention to incorporating energy efficient separation techniques such as adsorption in in situ product recovery (ISPR) approaches. This thesis focused on the characterization of two novel adsorbents for the recovery of alcohol biofuels from model aqueous solutions. First, a hydrophobic silica aerogel was evaluated as a biofuel adsorbent through characterization of equilibrium behavior for conventional second generation biofuels (e.g., ethanol and n-butanol). Longer chain and accordingly more hydrophobic alcohols (i.e., n-butanol and 2-pentanol) were more effectively adsorbed than shorter chain alcohols (i.e., ethanol and i-propanol), suggesting a mechanism of hydrophobic adsorption. Still, the adsorbed alcohol capacity at biologically relevant conditions were low relative to other `model' biofuel adsorbents as a result of poor interfacial contact between the aqueous and sorbent. However, sorbent wettability and adsorption is greatly enhanced at high concentrations of alcohol in the aqueous. Consequently, the sorbent exhibits Type IV adsorption isotherms for all biofuels studied, which results from significant multilayer adsorption at elevated alcohol concentrations in the aqueous. Additionally, sorbent wettability significantly affects the dynamic binding efficiency within a packed adsorption column. Second, mesoporous carbons were evaluated as biofuel adsorbents through characterization of equilibrium and kinetic behavior. Variations in synthetic conditions enabled tuning of specific surface area and pore morphology of adsorbents. The adsorbed alcohol capacity increased with elevated specific surface area of the adsorbents. While their adsorption capacity is comparable to polymeric adsorbents of similar surface area, pore morphology and structure of mesoporous carbons greatly influenced adsorption rates. Multiple cycles of adsorbent regeneration rendered no impact on adsorption equilibrium or kinetics. The high chemical and thermal stability of mesoporous carbons provide potential significant advantages over other commonly examined biofuel adsorbents. Correspondingly, mesoporous carbons should be further studied for biofuel ISPR applications.
ContributorsLevario, Thomas (Author) / Nielsen, David R (Thesis advisor) / Vogt, Bryan D (Committee member) / Lind, Mary L (Committee member) / Arizona State University (Publisher)
Created2011
Description
The world is grappling with two serious issues related to energy and climate change. The use of solar energy is receiving much attention due to its potential as one of the solutions. Air conditioning is particularly attractive as a solar energy application because of the near coincidence of peak cooling loads with the available solar power. Recently, researchers have started serious discussions of using adsorptive processes for refrigeration and heat pumps. There is some success for the >100 ton adsorption systems but none exists in the <10 ton size range required for residential air conditioning. There are myriad reasons for the lack of small-scale systems such as low Coefficient of Performance (COP), high capital cost, scalability, and limited performance data. A numerical model to simulate an adsorption system was developed and its performance was compared with similar thermal-powered systems. Results showed that both the adsorption and absorption systems provide equal cooling capacity for a driving temperature range of 70-120 ºC, but the adsorption system is the only system to deliver cooling at temperatures below 65 ºC. Additionally, the absorption and desiccant systems provide better COP at low temperatures, but the COP's of the three systems converge at higher regeneration temperatures. To further investigate the viability of solar-powered heat pump systems, an hourly building load simulation was developed for a single-family house in the Phoenix metropolitan area. Thermal as well as economic performance comparison was conducted for adsorption, absorption, and solar photovoltaic (PV) powered vapor compression systems for a range of solar collector area and storage capacity. The results showed that for a small collector area, solar PV is more cost-effective whereas adsorption is better than absorption for larger collector area. The optimum solar collector area and the storage size were determined for each type of solar system. As part of this dissertation work, a small-scale proof-of-concept prototype of the adsorption system was assembled using some novel heat transfer enhancement strategies. Activated carbon and butane was chosen as the adsorbent-refrigerant pair. It was found that a COP of 0.12 and a cooling capacity of 89.6 W can be achieved.
ContributorsGupta, Yeshpal (Author) / Phelan, Patrick E (Thesis advisor) / Bryan, Harvey J. (Committee member) / Mikellidas, Pavlos G (Committee member) / Pacheco, Jose R (Committee member) / Trimble, Steven W (Committee member) / Arizona State University (Publisher)
Created2011
Description
This dissertation presents a systematic study of the sorption mechanisms of hydrophobic silica aerogel (Cabot Nanogel®) granules for oil and volatile organic compounds (VOCs) in different phases. The performance of Nanogel for removing oil from laboratory synthetic oil-in-water emulsions and real oily wastewater, and VOCs from their aqueous solution, in both packed bed (PB) and inverse fluidized bed (IFB) modes was also investigated. The sorption mechanisms of VOCs in the vapor, pure liquid, and aqueous solution phases, free oil, emulsified oil, and oil from real wastewater on Nanogel were systematically studied via batch kinetics and equilibrium experiments. The VOC results show that the adsorption of vapor is very slow due to the extremely low thermal conductivity of Nanogel. The faster adsorption rates in the liquid and solution phases are controlled by the mass transport, either by capillary flow or by vapor diffusion/adsorption. The oil results show that Nanogel has a very high capacity for adsorption of pure oils. However, the rate for adsorption of oil from an oil-water emulsion on the Nanogel is 5-10 times slower than that for adsorption of pure oils or organics from their aqueous solutions. For an oil-water emulsion, the oil adsorption capacity decreases with an increasing proportion of the surfactant added. An even lower sorption capacity and a slower sorption rate were observed for a real oily wastewater sample due to the high stability and very small droplet size of the wastewater. The performance of Nanogel granules for removing emulsified oil, oil from real oily wastewater, and toluene at low concentrations in both PB and IFB modes was systematically investigated. The hydrodynamics characteristics of the Nanogel granules in an IFB were studied by measuring the pressure drop and bed expansion with superficial water velocity. The density of the Nanogel granules was calculated from the plateau pressure drop of the IFB. The oil/toluene removal efficiency and the capacity of the Nanogel granules in the PB or IFB were also measured experimentally and predicted by two models based on equilibrium and kinetic batch measurements of the Nanogel granules.
ContributorsWang, Ding (Author) / Lin, Jerry Y.S. (Thesis advisor) / Pfeffer, Robert (Thesis advisor) / Westerhoff, Paul (Committee member) / Nielsen, David (Committee member) / Lind, Mary Laura (Committee member) / Arizona State University (Publisher)
Created2011
Description
The use of petroleum for liquid-transportation fuels has strained the environment and caused the global crude oil reserves to diminish. Therefore, there exists a need to replace petroleum as the primary fuel derivative. Butanol is a four-carbon alcohol that can be used to effectively replace gasoline without changing the current automotive infrastructure. Additionally, butanol offers the same environmentally friendly effects as ethanol, but possess a 23% higher energy density. Clostridium acetobutylicum is an anaerobic bacterium that can ferment renewable biomass-derived sugars into butanol. However, this fermentation becomes limited by relatively low butanol concentrations (1.3% w/v), making this process uneconomical. To economically produce butanol, the in-situ product removal (ISPR) strategy is employed to the butanol fermentation. ISPR entails the removal of butanol as it is produced, effectively avoiding the toxicity limit and allowing for increased overall butanol production. This thesis explores the application of ISPR through integration of expanded-bed adsorption (EBA) with the C. acetobutylicum butanol fermentations. The goal is to enhance volumetric productivity and to develop a semi-continuous biofuel production process. The hydrophobic polymer resin adsorbent Dowex Optipore L-493 was characterized in cell-free studies to determine the impact of adsorbent mass and circulation rate on butanol loading capacity and removal rate. Additionally, the EBA column was optimized to use a superficial velocity of 9.5 cm/min and a resin fraction of 50 g/L. When EBA was applied to a fed-batch butanol fermentation performed under optimal operating conditions, a total of 25.5 g butanol was produced in 120 h, corresponding to an average yield on glucose of 18.6%. At this level, integration of EBA for in situ butanol recovered enabled the production of 33% more butanol than the control fermentation. These results are very promising for the production of butanol as a biofuel. Future work will entail the optimization of the fed-batch process for higher glucose utilization and development of a reliable butanol recovery system from the resin.
ContributorsWiehn, Michael (Author) / Nielsen, David (Thesis advisor) / Lin, Jerry (Committee member) / Lind, Mary Laura (Committee member) / Arizona State University (Publisher)
Created2013
Description
Plastics, when released into the environment, undergo surface weathering due to mechanical abrasion and ultraviolet (UV) exposure that leads to the formation of microplastics. Weathering also introduces oxygen functional groups on the surface, which will affect surface interactions compared to pristine plastics. In this study, the adsorption of selected model contaminants of high environmental relevance was evaluated at different level of abiotic and biotic transformation to understand how microplastics aging influences contaminant adsorption on high density polyethylene (HDPE) and polypropylene (PPE). Microplastics were aged through an accelerated weathering process using UV exposure with or without hydrogen peroxide. The effect of UV aging on the microplastics’ morphology and surface chemistry was characterized by Fourier Transform Infrared Spectroscopy, X-Ray Photoelectron Spectroscopy, streaming Zeta potential, Brunauer–Emmett–Teller Krypton adsorption analyses and Computed X-Ray Tomography. Sorption of organic contaminants was found to be higher on aged microplastics compared to pristine ones for all contaminants investigated. This increase in sorption affinity was found to be associated with a change in the surface chemistry and not in an increase in specific surface area after aging. Biological surface weathering (i.e., biofilm formation) was carried out at a lab-scale setting using model biofilm-forming bacteria followed by adsorption affinity measurement of biofilm-laden microplastics with the model organic contaminants. The amount of microbial biomass accumulated on the surface was also evaluated to correlate the changes in sorption affinity with the change in microplastic biofilm formation. The results of this study emphasize the need to understand how contaminant-microplastics interactions will evolve as microplastics are altered by biotic and abiotic factors in the environment.
ContributorsBhagat, Kartik (Author) / Perreault, Francois (Thesis advisor) / Westerhoff, Paul (Committee member) / Oswald, Jay (Committee member) / Arizona State University (Publisher)
Created2022
Description
The objective of this research was to develop Aluminophosphate-five (AlPO4-5, AFI) zeolite adsorbents for efficient oxygen removal from a process stream to support an on-going Department of Energy (DOE) project on solar energy storage. A molecular simulation study predicted that substituted AlPO4-5 zeolite can adsorb O2 through a weak chemical bond at ambient temperature. Substituted AlPO4-5 zeolite was successfully synthesized via hydrothermal crystallization by following carefully designed procedures to tailor the zeolite for efficient O2 adsorption. Synthesized AlPO4-5 in this work included Sn/AlPO-5, Mo/AlPO-5, Pd/AlPO-5, Si/AlPO-5, Mn/AlPO-5, Ce/AlPO-5, Fe/AlPO-5, CuCe/AlPO-5, and MnSnSi/AlPO-5. While not all zeolite samples synthesized were fully characterized, selected zeolite samples were characterized by powder x-ray diffraction (XRD) for crystal structure confirmation and phase identification, and nitrogen adsorption for their pore textural properties. The Brunauer-Emmett-Teller (BET) specific surface area and pore size distribution were between 172 m2 /g - 306 m2 /g and 6Å - 9Å, respectively, for most of the zeolites synthesized. Samples of great interest to this project such as Sn/AlPO-5, Mo/AlPO-5 and MnSnSi/AlPO-5 were also characterized using x-ray photoelectron spectroscopy (XPS) and energy-dispersive x-ray spectroscopy (EDS) for elemental analysis, scanning electron microscopy (SEM) for morphology and particle size estimation, and electron paramagnetic resonance (EPR) for nature of adsorbed oxygen. Oxygen and nitrogen adsorption experiments were carried out in a 3-Flex adsorption apparatus (Micrometrics) at various temperatures (primarily at 25℃) to determine the adsorption properties of these zeolite samples as potential adsorbents for oxygen/nitrogen separation. Experiments showed that some of the zeolite samples adsorb little-to-no oxygen and nitrogen at 25℃, while other zeolites such as Sn/AlPO-5, Mo/AlPO-5, and MnSnSi/AlPO-5 adsorb decent but inconsistent amounts of oxygen with the highest observed values of about 0.47 mmol/ g, 0.56 mmol/g, and 0.84 mmol/ g respectively. The inconsistency in adsorption is currently attributed to non-uniform doping of the zeolites, and these findings validate that some substituted AlPO4-5 zeolites are promising adsorbents. However, more investigations are needed to verify the causes of this inconsistency to develop a successful AlPO4-5 zeolite-based adsorbent for oxygen/nitrogen separation.
ContributorsBuyinza, Allan Smith (Author) / Deng, Shuguang (Thesis advisor) / Varman, Arul M (Committee member) / Jin, Kailong (Committee member) / Arizona State University (Publisher)
Created2021
Description
Adsorption is fundamentally known to be a non-isothermal process; in which temperature increase is largely significant, causing fairly appreciable impacts on the processkinetics. For porous adsorbent particles like metal organic frameworks (MOFs), silica
gel, and zeolite, the resultant relative heat generated is partly distributed within the
particle, and the rest is transferred to the surrounding ambient fluid (air).
For large step changes in adsorbed phase concentration and fast adsorption rates,
especially, the isothermality of adsorption (as in some studies) is an inadequate assumption and inspires rather erroneous diffusivities of porous adsorbents. Isothermal models, in consequence, are insufficient for studying adsorption in porous adsorbents. Non-isothermal models can satisfactorily and exhaustively describe adsorption
in porous adsorbents. However, in many of the analyses done using the models, the
thermal conductivity of the adsorbent is assumed to be infinite; thus, particle temperature is taken to be fairly uniform during the process—a trend not observed for
carbon dioxide (CO2) adsorption on MOFs.
A new and detailed analysis of CO2 adsorption in a single microporous MOF-5
particle, assuming a finite effective thermal conductivity along with comprehensive
parametric studies for the models, is presented herein. A significant average temperature increase of 5K was calculated using the new model, compared to the 0.7K
obtained using the Stremming model. A corresponding increase in diffusivity from
8.17 x 10-13 to 1.72 x 10-11 m2/s was observed, indicating the limitations of both
isothermal models and models that assume constant diffusivity.
ContributorsNkuutu, John (Author) / Lin, Jerry (Thesis advisor) / Emady, Heather (Committee member) / Deng, Shuguang (Committee member) / Arizona State University (Publisher)
Created2023
Description
Anthropogenic processes have increased the concentration of toxic Se, As and N in water. Oxo-anions of these species are poisonous to aquatic and terrestrial life. Current remediation techniques have low selectivity towards their removal. Understanding the chemistry and physics which control oxo-anion adsorption on metal oxide and the catalytic nitrate reduction to inform improved remediation technologies can be done using Density functional theory (DFT) calculations. The adsorption of selenate, selenite, and arsenate was investigated on the alumina and hematite to inform sorbent design strategies. Adsorption energies were calculated as a function of surface structure, composition, binding motif, and pH within a hybrid implicit-explicit solvation strategy. Correlations between surface property descriptors including water network structure, cationic species identity, and facet and the adsorption energies of the ions show that the surface water network controls the adsorption energy more than any other, including the cationic species of the metal-oxide. Additionally, to achieve selectivity for selenate over sulphate, differences in their electronic structure must be exploited, for example by the reduction of selenate to selenite by Ti3+ cations.
Thermochemical or electrochemical reduction pathways to convert NO3- to N2 or NH3, which are benign or value-added products, respectively are examined over single-atom electrocatalysts (SAC) in Cu. The activity and selectivity for nitrate reduction are compared with the competitive hydrogen evolution reaction (HER). Cu suppresses HER but produces toxic NO2- because of a high activation barrier for cleaving the second N-O bond. SACs provide secondary sites for reaction and break traditional linear scaling relationships. Ru-SACs selectively produce NH3 because N-O bond scission is facile, and the resulting N remains isolated on SAC sites; reacting with H+ from solvating H2O to form ammonia. Conversely, Pd-SAC forms N2 because the reduced N* atoms migrate to the Cu surface, which has a low H availability, allowing N atoms to combine to N2. This relation between N* binding preference and reduction product is demonstrated across an array of SAC elements.
Hence, the solvation effects on the surface critically alter the activity of adsorption and catalysis and the removal of toxic pollutants can be improved by altering the surface water network.
ContributorsGupta, Srishti (Author) / Muhich, Christopher L (Thesis advisor) / Singh, Arunima (Committee member) / Emady, Heather (Committee member) / Westerhoff, Paul (Committee member) / Deng, Shuguang (Committee member) / Arizona State University (Publisher)
Created2023
Description
Generally, porous structures are nano-enabled with a high loading of nanoparticles (NPs) to enhance adsorption capacity, but pore blockage plays a determinant role in kinetics in this approach. The goal of this study is to investigate the effect of NPs loading on the adsorption kinetics and capacity of titanium dioxide (TiO2). To accomplish this, side-emitting optical fibers impregnated with different mass loadings of TiO2 (Ti-NIFs) were developed and characterized. Additionally, taking advantage of the use of optical fibers, the potential influence of ultraviolet light (UV) irradiation in arsenate adsorption over TiO2 was studied. The adsorption kinetics and capacity of Ti-NIFs were compared with slurry TiO2 nanoparticles in batch reactors. Arsenate adsorption was evaluated under both UV irradiation and dark conditions. The Ti-NIF with the lowest TiO2 loading showed comparable adsorption rate to NPs in suspension. Higher loadings resulted in high mass-transfer limitations. Interestingly, the normalized adsorption capacity of the produced Ti-NIFs maintained the adsorption capacity similar as they were freely dispersed. The experiments showed that UV has no influence in arsenate adsorption onto TiO2, contrary to previous literature indicating a positive effect, which was likely due to pH drift. Overall, this study shows that loadings of nanoparticles below 1% effectively enhance nano-enabled surfaces' performance.
ContributorsGonzalez Rodriguez, Jose Ricardo (Author) / Westerhoff, Paul (Thesis advisor) / Garcia-Segura, Sergi (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2023
Description
Just for a moment! Imagine you live in Arizona without air-conditioning systems!
Air-conditioning and refrigeration systems are one of the most crucial systems in anyone’s house and car these days. Energy resources are becoming more scarce and expensive. Most of the currently used refrigerants have brought an international concern about global warming. The search for more efficient cooling/refrigeration systems with environmental friendly refrigerants has become more and more important so as to reduce greenhouse gas emissions and ensure sustainable and affordable energy systems. The most widely used air-conditioning and refrigeration system, based on the vapor compression cycle, is driven by converting electricity into mechanical work which is a high quality type of energy. However, these systems can instead be possibly driven by heat, be made solid-state (i.e., thermoelectric cooling), consist entirely of a gaseous working fluid (i.e., reverse Brayton cycle), etc. This research explores several thermally driven cooling systems in order to understand and further overcome some of the major drawbacks associated with their performance as well as their high capital costs. In the second chapter, we investigate the opportunities for integrating single- and double-stage ammonia-water (NH3–H2O) absorption refrigeration systems with multi-effect distillation (MED) via cascade of rejected heat for large-scale plants. Similarly, in the third chapter, we explore a new polygeneration cooling-power cycle’s performance based on Rankine, reverse Brayton, ejector, and liquid desiccant cycles to produce power, cooling, and possibly fresh water for various configurations. Different configurations are considered from an energy perspective and are compared to stand-alone systems. In the last chapter, a new simple, inexpensive, scalable, environmentally friendly cooling system based on an adsorption heat pump system and evacuated tube solar collector is experimentally and theoretically studied. The system is destined as a small-scale system to harness solar radiation to provide a cooling effect directly in one system.
Air-conditioning and refrigeration systems are one of the most crucial systems in anyone’s house and car these days. Energy resources are becoming more scarce and expensive. Most of the currently used refrigerants have brought an international concern about global warming. The search for more efficient cooling/refrigeration systems with environmental friendly refrigerants has become more and more important so as to reduce greenhouse gas emissions and ensure sustainable and affordable energy systems. The most widely used air-conditioning and refrigeration system, based on the vapor compression cycle, is driven by converting electricity into mechanical work which is a high quality type of energy. However, these systems can instead be possibly driven by heat, be made solid-state (i.e., thermoelectric cooling), consist entirely of a gaseous working fluid (i.e., reverse Brayton cycle), etc. This research explores several thermally driven cooling systems in order to understand and further overcome some of the major drawbacks associated with their performance as well as their high capital costs. In the second chapter, we investigate the opportunities for integrating single- and double-stage ammonia-water (NH3–H2O) absorption refrigeration systems with multi-effect distillation (MED) via cascade of rejected heat for large-scale plants. Similarly, in the third chapter, we explore a new polygeneration cooling-power cycle’s performance based on Rankine, reverse Brayton, ejector, and liquid desiccant cycles to produce power, cooling, and possibly fresh water for various configurations. Different configurations are considered from an energy perspective and are compared to stand-alone systems. In the last chapter, a new simple, inexpensive, scalable, environmentally friendly cooling system based on an adsorption heat pump system and evacuated tube solar collector is experimentally and theoretically studied. The system is destined as a small-scale system to harness solar radiation to provide a cooling effect directly in one system.
ContributorsAlelyani, Sami M (Author) / Phelan, Patrick E (Thesis advisor) / Wang, Liping (Committee member) / Stechel, Ellen B (Committee member) / Calhoun, Ronald J (Committee member) / Alalili, Ali R (Committee member) / Arizona State University (Publisher)
Created2018