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- All Subjects: chemical engineering
- Creators: Chemical Engineering Program
- Status: Published
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
Membrane technology is a viable option to debottleneck distillation processes and minimize the energy burden associated with light hydrocarbon mixture separations. Zeolitic imidazolate frameworks (ZIFs) are a new class of microporous metal-organic frameworks with highly tailorable zeolitic pores and unprecedented separation characteristics. ZIF-8 membranes demonstrate superior separation performance for propylene/propane (C3) and hydrogen/hydrocarbon mixtures at room temperature. However, to date, little is known about the static thermal stability and ethylene/ethane (C2) separation characteristics of ZIF-8. This dissertation presents a set of fundamental studies to investigate the thermal stability, transport and modification of ZIF-8 membranes for light hydrocarbon separations.
Static TGA decomposition kinetics studies show that ZIF-8 nanocrystals maintain their crystallinity up to 200○C in inert, oxidizing and reducing atmospheres. At temperatures of 250○C and higher, the findings herein support the postulation that ZIF-8 nanocrystals undergo temperature induced decomposition via thermolytic bond cleaving reactions to form an imidazole-Zn-azirine structure. The crystallinity/bond integrity of ZIF-8 membrane thin films is maintained at temperatures below 150○C.
Ethane and ethylene transport was studied in single and binary gas mixtures. Thermodynamic parameters derived from membrane permeation and crystal adsorption experiments show that the C2 transport mechanism is controlled by adsorption rather than diffusion. Low activation energy of diffusion values for both C2 molecules and limited energetic/entropic diffusive selectivity are observed for C2 molecules despite being larger than the nominal ZIF-8 pore aperture and is due to pore flexibility.
Finally, ZIF-8 membranes were modified with 5,6 dimethylbenzimidazole through solvent assisted membrane surface ligand exchange to narrow the pore aperture for enhanced molecular sieving. Results show that relatively fast exchange kinetics occur at the mainly at the outer ZIF-8 membrane surface between 0-30 minutes of exchange. Short-time exchange enables C3 selectivity increases with minimal olefin permeance losses. As the reaction proceeds, the ligand exchange rate slows as the 5,6 DMBIm linker proceeds into the ZIF-8 inner surface, exchanges with the original linker and first disrupts the original framework’s crystallinity, then increases order as the reaction proceeds. The ligand exchange rate increases with temperature and the H2/C2 separation factor increases with increases in ligand exchange time and temperature.
Static TGA decomposition kinetics studies show that ZIF-8 nanocrystals maintain their crystallinity up to 200○C in inert, oxidizing and reducing atmospheres. At temperatures of 250○C and higher, the findings herein support the postulation that ZIF-8 nanocrystals undergo temperature induced decomposition via thermolytic bond cleaving reactions to form an imidazole-Zn-azirine structure. The crystallinity/bond integrity of ZIF-8 membrane thin films is maintained at temperatures below 150○C.
Ethane and ethylene transport was studied in single and binary gas mixtures. Thermodynamic parameters derived from membrane permeation and crystal adsorption experiments show that the C2 transport mechanism is controlled by adsorption rather than diffusion. Low activation energy of diffusion values for both C2 molecules and limited energetic/entropic diffusive selectivity are observed for C2 molecules despite being larger than the nominal ZIF-8 pore aperture and is due to pore flexibility.
Finally, ZIF-8 membranes were modified with 5,6 dimethylbenzimidazole through solvent assisted membrane surface ligand exchange to narrow the pore aperture for enhanced molecular sieving. Results show that relatively fast exchange kinetics occur at the mainly at the outer ZIF-8 membrane surface between 0-30 minutes of exchange. Short-time exchange enables C3 selectivity increases with minimal olefin permeance losses. As the reaction proceeds, the ligand exchange rate slows as the 5,6 DMBIm linker proceeds into the ZIF-8 inner surface, exchanges with the original linker and first disrupts the original framework’s crystallinity, then increases order as the reaction proceeds. The ligand exchange rate increases with temperature and the H2/C2 separation factor increases with increases in ligand exchange time and temperature.
ContributorsJames, Joshua B. (Author) / Lin, Jerry Y.S. (Thesis advisor) / Emady, Heather (Committee member) / Lind, Mary Laura (Committee member) / Mu, Bin (Committee member) / Seo, Dong (Committee member) / Arizona State University (Publisher)
Created2017
Description
Graphene oxide membranes have shown promising gas separation characteristics specially for hydrogen that make them of interest for industrial applications. However, the gas transport mechanism for these membranes is unclear due to inconsistent permeation and separation results reported in literature. Graphene oxide membranes made by filtration, the most common synthesis method, contain wrinkles affecting their gas separation characteristics and the method itself is difficult to scale up. Moreover, the production of graphene oxide membranes with fine-tuned interlayer spacing for improved molecular separation is still a challenge. These unsolved issues will affect their potential impact on industrial gas separation applications.
In this study, high quality graphene oxide membranes are synthesized on polyester track etch substrates by different deposition methods and characterized by XRD, SEM, AFM as well as single gas permeation and binary (H2/CO2) separation experiments. Membranes are made from large graphene oxide sheets of different sizes (33 and 17 micron) using vacuum filtration to shed more light on their transport mechanism. Membranes are made from dilute graphene oxide suspension by easily scalable spray coating technique to minimize extrinsic wrinkle formation. Finally, Brodie’s derived graphene oxide sheets were used to prepare membranes with narrow interlayer spacing to improve their (H2/CO2) separation performance.
An inter-sheet and inner-sheet two-pathway model is proposed to explain the permeation and separation results of graphene oxide membranes obtained in this study. At room temperature, large gas molecules (CH4, N2, and CO2) permeate through inter-sheet pathway of the membranes, exhibiting Knudsen like diffusion characteristics, with the permeance for the small sheet membrane about twice that for the large sheet membrane. The small gases (H2 and He) exhibit much higher permeance, showing significant flow through an inner-sheet pathway, in addition to the flow through the inter-sheet pathway. Membranes prepared by spray coating offer gas characteristics similar to those made by filtration, however using dilute graphene oxide suspension in spray coating will help reduce the formation of extrinsic wrinkles which result in reduction in the porosity of the inter-sheet pathway where the transport of large gas molecules dominates. Brodie’s derived graphene oxide membranes showed overall low permeability and significant improvement in in H2/CO2 selectivity compared to membranes made using Hummers’ derived sheets due to smaller interlayer space height of Brodie’s sheets (~3 Å).
In this study, high quality graphene oxide membranes are synthesized on polyester track etch substrates by different deposition methods and characterized by XRD, SEM, AFM as well as single gas permeation and binary (H2/CO2) separation experiments. Membranes are made from large graphene oxide sheets of different sizes (33 and 17 micron) using vacuum filtration to shed more light on their transport mechanism. Membranes are made from dilute graphene oxide suspension by easily scalable spray coating technique to minimize extrinsic wrinkle formation. Finally, Brodie’s derived graphene oxide sheets were used to prepare membranes with narrow interlayer spacing to improve their (H2/CO2) separation performance.
An inter-sheet and inner-sheet two-pathway model is proposed to explain the permeation and separation results of graphene oxide membranes obtained in this study. At room temperature, large gas molecules (CH4, N2, and CO2) permeate through inter-sheet pathway of the membranes, exhibiting Knudsen like diffusion characteristics, with the permeance for the small sheet membrane about twice that for the large sheet membrane. The small gases (H2 and He) exhibit much higher permeance, showing significant flow through an inner-sheet pathway, in addition to the flow through the inter-sheet pathway. Membranes prepared by spray coating offer gas characteristics similar to those made by filtration, however using dilute graphene oxide suspension in spray coating will help reduce the formation of extrinsic wrinkles which result in reduction in the porosity of the inter-sheet pathway where the transport of large gas molecules dominates. Brodie’s derived graphene oxide membranes showed overall low permeability and significant improvement in in H2/CO2 selectivity compared to membranes made using Hummers’ derived sheets due to smaller interlayer space height of Brodie’s sheets (~3 Å).
ContributorsIbrahim, Amr Fatehy Muhammad (Author) / Lin, Jerry Y.S. (Thesis advisor) / Mu, Bin (Committee member) / Lind, Mary (Committee member) / Green, Matthew (Committee member) / Wang, Qing (Committee member) / Arizona State University (Publisher)
Created2018
Targeting Tumors: Inclusion of Functional Groups on Ion-Containing Block Copolymers to Combat Cancer
Description
This research attempts to determine the most effective method of synthesizing a peptide such that it can be utilized as a targeting moiety for polymeric micelles. Two melanoma-associated peptides with high in vitro and in vivo binding affinity for TNF receptors have been identified and synthesized. Matrix Assisted Laser Desorption/Ionization-Time of Flight Mass Spectrometry (MALDI-ToF) was used to help verify the structure of both peptides, which were purified using Reversed-Phase High Performance Liquid Chromatography (RP-HPLC). The next steps in the research are to attach the peptides to a micelle and determine their impact on micelle stability.
ContributorsMoe, Anna Marguerite (Author) / Green, Matthew (Thesis director) / Jones, Anne (Committee member) / Sullivan, Millicent (Committee member) / Chemical Engineering Program (Contributor) / School of International Letters and Cultures (Contributor) / Sandra Day O'Connor College of Law (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
The mechanisms of extracellular respiration in Geobacter sulfurreducens, commonly considered to be a model organism for anode respiration, are yet to be completely understood. The interplay between electron and proton transport especially could be a key to gaining further insights. One way to investigate the mechanisms of extracellular respiration under varying environmental conditions is by analyzing the electrochemical response of the biofilm with respect to pH, buffer concentrations, and acetate concentrations. I seek to increase the understanding of the electrochemical response of the G. sulfurreducens biofilm through electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques in concert with chronoamperometry. I used Geobacter sulfurreducens PCA biofilms in single-chamber electrochemical cells (approximately 100 mL volume) with a small gold working electrode (3.14 mm2). I observed limitations in the initial methods used for media replacement. I tracked changes in the CV data, such as EKA (midpoint potential), as a function of pH and buffer concentration. The media replacement method developed demonstrates success in pH experiments that will be transferrable to other environmental conditions to study electron transport. The experiments revealed that the clarity of data collected is dependent on the quality of the biofilm. A high quality biofilm is characterized by a high current density and normal growth behavior. The general trends seen in these experiments are that as pH increases the potential decreases, and as buffer concentration increases the potential decreases and pH increases. Acetate-free conditions in the reactor were unable to be achieved as characterized by non-zero current densities in the acetate-free experiments.
ContributorsHolzer, Denton Gene (Author) / Torres, Cesar (Thesis director) / Popat, Sudeep (Committee member) / Yoho, Rachel (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Lithium-ion batteries are the predominant source of electrical energy storage for most portable electronics applications, including hybrid/electric vehicles, laptops, and cellular phones. However, these batteries pose safety concerns due to their flammability and tendency to violently ignite upon short circuiting or failing. Solid electrolytes are a current research development aimed at reducing the flammability and reactivity of lithium batteries. The compound Li7La3Zr2O12, or LLZO, exhibits satisfactory ionic conductivity in the cubic phase, which is normally synthesized via doping with Al. It has recently been discovered that synthesizing nanostructured LLZO can stabilize the cubic phase without the need for doping. Here nanostructured LLZO was formed using templating on various cellulosic fibers, including cotton fibers, printer paper, filter paper, and nanocellulose fibrils followed by calcination at 700-800 °C. The effect of templating material, calcination temperature, calcination time, and heating ramp rate on LLZO phase and morphology was thoroughly investigated. Templating was determined to be an effective method for controlling the LLZO size and morphology, and most templating experiments resulted in LLZO fibers or ligaments similar in size and morphology to the original template material. A systematic study on the various experimental parameters was performed, concluding that low calcination time and low ramp rate favored smaller ligament formation. Further, it was verified that cubic phase stabilization occurred for LLZO with ligaments of less than 1 micron on average without the use of doping. This research provides more information regarding the size dependence on cubic LLZO stabilization that has not been previously investigated in detail.
ContributorsGordon, Zachary Daniel (Author) / Chan, Candace K. (Thesis director) / Lin, Jerry (Committee member) / Barrett, The Honors College (Contributor) / School of Mathematical and Statistical Sciences (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05
Description
The goal of this research project is to create a mixed matrix membrane that can withstand very acidic environments but still be used to purify water. The ultimate goal of this membrane is to be used to purify urine both here on Earth and in space. The membrane would be able to withstand these harsh conditions due the incorporation of a resilient impermeable polymer layer that will be cast above the lower hydrophilic layer. Nanoparticles called zeolites will act as a water selective pathway through this impermeable layer and allow water to flow through the membrane. This membrane will be made using a variety of methods and polymers to determine both the cheapest and most effective way of creating this chemical resistant membrane. If this research is successful, many more water sources can be tapped since the membranes will be able to withstand hard conditions. This document is primarily focused on our progress on the development of a highly permeable polymer-zeolite film that makes up the bottom layer of the membrane. Multiple types of casting methods were investigated and it was determined that spin coating at 4000 rpm was the most effective. Based on a literature review, we selected silicalite-1 zeolites as the water-selective nanoparticle component dispersed in a casting solution of polyacrylonitrile in N-methylpyrrolidinone to comprise this hydrophilic layer. We varied the casting conditions of several simple solution-casting methods to produce thin films on the porous substrate with optimal film properties for our membrane design. We then cast this solution on other types of support materials that are more flexible and inexpensive to determine which combination resulted in the thinnest and most permeable film.
ContributorsHerrera, Sofia Carolina (Author) / Lind, Mary Laura (Thesis director) / Khosravi, Afsaneh (Committee member) / Hestekin, Jamie (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05
Description
In our modern world the source of for many chemicals is to acquire and refine oil. This process is becoming an expensive to the environment and to human health. Alternative processes for acquiring the final product have been developed but still need work. One product that is valuable is butanol. The normal process for butanol production is very intensive but there is a method to produce butanol from bacteria. This process is better because it is more environmentally safe than using oil. One problem however is that when the bacteria produce too much butanol it reaches the toxicity limit and stops the production of butanol. In order to keep butanol from reaching the toxicity limit an adsorbent is used to remove the butanol without harming the bacteria. The adsorbent is a mesoporous carbon powder that allows the butanol to be adsorbed on it. This thesis explores different designs for a magnetic separation process to extract the carbon powder from the culture.
ContributorsChabra, Rohin (Author) / Nielsen, David (Thesis director) / Torres, Cesar (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05
Description
One of the primary bottlenecks to chemical production in biological organisms is the toxicity of the chemical. Overexpression of efflux pumps has been shown to increase tolerance to aromatic compounds such as styrene and styrene oxide. Tight control of pump expression is necessary to maximize titers and prevent excessive strain on the cells. This study aimed to identify aromatic-sensitive native promoters and heterologous biosensors for construction of closed-loop control of efflux pump expression in E. coli. Using a promoter library constructed by Zaslaver et al., activation was measured through GFP output. Promoters were evaluated for their sensitivity to the addition of one of four aromatic compounds, their "leaking" of signal, and their induction threshold. Out of 43 targeted promoters, 4 promoters (cmr, mdtG, yahN, yajR) for styrene oxide, 2 promoters (mdtG, yahN) for styrene, 0 promoters for 2-phenylethanol, and 1 promoter for phenol (pheP) were identified as ideal control elements in aromatic bioproduction. In addition, a series of three biosensors (NahR, XylS, DmpR) known to be inducible by other aromatics were screened against styrene oxide, 2-phenylethanol, and phenol. The targeted application of these biosensors is aromatic-induced activation of linked efflux pumps. All three biosensors responded strongly in the presence of styrene oxide and 2-phenylethanol, with minor activation in the presence of phenol. Bioproduction of aromatics continues to gain traction in the biotechnology industry, and the continued discovery of aromatic-inducible elements will be essential to effective pathway control.
ContributorsXu, Jimmy (Author) / Nielsen, David (Thesis director) / Wang, Xuan (Committee member) / School of Life Sciences (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
Asymmetric polystyrene-gold composite particles are successfully synthesized alongside core-shell composite particles via a one-step Pickering emulsion polymerization method. Unlike core-shell particles which form in the droplet phase of a stabilized Pickering emulsion, asymmetric particles form via a seeded growth mechanism. These composite particles act as catalysts with higher recyclability than pure gold nanoparticles due to reduced agglomeration. With the addition of N-isopropylacrylamide (NIPAAM) monomers, temperature-responsive asymmetric and core-shell polystyrene/poly(N-isopropylacrylamide)-gold composite particles are also synthesized via Pickering emulsion polymerization. The asymmetric particles have a greater thermo-responsiveness than the core-shell particles due to the increased presence of NIPAAM monomers in the seeded-growth formation. Poly(N-isopropylacrylamide) (PNIPAM)-containing asymmetric particles have tunable rheological and optical properties due to their significant size decrease above the lower critical solution temperature (LCST).
ContributorsRabiah, Noelle Ibrahim (Author) / Dai, Lenore (Thesis director) / Torres, Cesar (Committee member) / Zhang, Mingmeng (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05