Matching Items (8)
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- All Subjects: Membranes
- Creators: Lin, Jerry
- Creators: Green, Matthew D
- Creators: Green, Matthew D.
Description
In this research, construction of a model membrane system using Polyvinylidene Chloride-Co Acrylonitrile and Linde Type A zeolites is described. The systems aims to separate out flow through zeolite pores and flow through interfaces between zeolites and polymers through the use of pore filled and pore open zeolites. Permeation tests and salt rejection tests were performed, and the data analyzed to yield approximation of separated flow through zeolites and interfaces. This work concludes the more work is required to bring the model system into a functioning state. New polymer selections and new techniques to produce the membrane system are described for future work.
ContributorsShabilla, Andrew Daniel (Author) / Lind, Mary Laura (Thesis director) / Lin, Jerry (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05
Description
Amine-modified solid sorbents and membrane separation are promising technologies for separation and capture of carbon dioxide (CO2) from combustion flue gas. Amine absorption processes are mature, but still have room for improvement. This work focused on the synthesis of amine-modified aerogels and metal-organic framework-5 (MOF-5) membranes for CO2 separation. A series of solid sorbents were synthesized by functionalizing amines on the surface of silica aerogels. This was done by three coating methods: physical adsorption, magnetically assisted impact coating (MAIC) and atomic layer deposition (ALD). CO2 adsorption capacity of the sorbents was measured at room temperature in a Cahn microbalance. The sorbents synthesized by physical adsorption show the largest CO2 adsorption capacity (1.43-1.63 mmol CO2/g). An additional sorbent synthesized by ALD on hydrophilic aerogels at atmospheric pressures shows an adsorption capacity of 1.23 mmol CO2/g. Studies on one amine-modified sorbent show that the powder is of agglomerate bubbling fluidization (ABF) type. The powder is difficult to fluidize and has limited bed expansion. The ultimate goal is to configure the amine-modified sorbents in a micro-jet assisted gas fluidized bed to conduct adsorption studies. MOF-5 membranes were synthesized on α-alumina supports by two methods: in situ synthesis and secondary growth synthesis. Characterization by scanning electron microscope (SEM) imaging and X-ray diffraction (XRD) show that the membranes prepared by both methods have a thickness of 14-16 μm, and a MOF-5 crystal size of 15-25 μm with no apparent orientation. Single gas permeation results indicate that the gas transport through both membranes is determined by a combination of Knudsen diffusion and viscous flow. The contribution of viscous flow indicates that the membranes have defects.
ContributorsRosa, Teresa M (Author) / Lin, Jerry (Thesis advisor) / Pfeffer, Robert (Thesis advisor) / Dai, Lenore (Committee member) / Nielsen, David (Committee member) / Arizona State University (Publisher)
Created2010
Description
Metal-organic frameworks (MOFs) are a new set of porous materials comprised of metals or metal clusters bonded together in a coordination system by organic linkers. They are becoming popular for gas separations due to their abilities to be tailored toward specific applications. Zirconium MOFs in particular are known for their high stability under standard temperature and pressure due to the strength of the Zirconium-Oxygen coordination bond. However, the acid modulator needed to ensure long range order of the product also prevents complete linker deprotonation. This leads to a powder product that cannot easily be incorporated into continuous MOF membranes. This study therefore implemented a new bi-phase synthesis technique with a deprotonating agent to achieve intergrowth in UiO-66 membranes. Crystal intergrowth will allow for effective gas separations and future permeation testing. During experimentation, successful intergrown UiO-66 membranes were synthesized and characterized. The degree of intergrowth and crystal orientations varied with changing deprotonating agent concentration, modulator concentration, and ligand:modulator ratios. Further studies will focus on achieving the same results on porous substrates.
ContributorsClose, Emily Charlotte (Author) / Mu, Bin (Thesis director) / Shan, Bohan (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
Description
This study details the construction and operation of a dry-jet wet spinning apparatus for extruding hollow fiber membranes (HFMs). The main components of the apparatus are a spinneret, a coagulation bath, and an automatic collection reel. Continuous fiber formation was achieved using two syringe pumps simultaneously delivering polymer dope and bore fluid to the spinneret. Based on apparatus runs performed with Polysulfone (PSF) dopes dissolved in N,N-Dimethylacetamide and supporting rheological analysis, the entanglement concentration, ce, was identified as a minimum processing threshold for creating HFMs. Similarly, significant increases in the ultimate tensile strength, fracture strain, and Young's modulus for extruded HFMs were observed as polymer dope concentration was increased at levels near ce. Beyond this initial increase, subsequent tests at higher PSF concentrations yielded diminishing changes in mechanical properties, suggesting an asymptotic approach to a point where the trend would cease. Without further research, it is theorized that this point falls on a transition from the semidiute entangled to concentrated concentration regimes. SEM imaging of samples revealed the formation of grooved structures on the inner surface of samples, which was determined to be a result of the low flowrate and polymer dope concentrations used in processing the HFMs during apparatus runs. Based on continued operation of the preliminary apparatus design, many areas of improvement were noted. Namely, these consisted of controlling the collector speed, eliminating rubbing of nascent fibers against the edge of the coagulation bath by installing an elevated roller, and replacing tygon tubing for the polymer line with a luer lock adapter for direct syringe attachment to the spinneret.
ContributorsBridge, Alexander Thomas (Author) / Green, Matthew D. (Thesis director) / Lin, Jerry Y. S. (Committee member) / School of Mathematical and Statistical Sciences (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2017-05
Description
The following thesis documents a two-fold approach to investigate challenges pertaining to water purification, first through a meta-analysis of ionic liquid toxicity, then through experimentation aimed at developing water pre-treatment membranes. Ionic liquids (ILs) are salts with low melting points, typically liquid at room temperature. Several extraordinary physical attributes, e.g. low viscosity, high conductivity, low to no vapor pressure, etc., and seemingly unlimited combinations available, have pushed IL research to the forefront of many research fronts. Concerns are raised as ionic liquids are rushed into commercial production without sufficient environmental regulation. Research has shown that the chemicals are in fact toxic, yet have developed a reputation for being “green” chemicals due to select physical attributes and applications. The meta-analysis discussed focuses on industry perception of ionic liquid toxicity through a patent review, and considers toxicity of ILs comparatively against other chemical families with well-established toxicity. The meta-analysis revealed that the total patent literature pertaining to ILs (n=3358) resulted in 112 patents that addressed the toxicity of ILs, and notably few (n=17) patents defined ILs as toxic, representing only 0.51% of the evaluated body of work on intellectual property claims. Additionally, toxicity of ionic liquids is comparable to that of other chemical families.
The objective of the experimentation was to explore the effect of crosslinker chain length on the morphology of nanofiber mats. Specifically, poly(vinyl alcohol (PVA) was electrospun into nanofiber mats and poly(ethylene) glycol bis(carboxylic acid) (PEG diacid) was used as the crosslinking agent. As-spun fibers had average fiber diameter of 70 ± 30 nm with an average pore size of 0.10 ± 0.16 μm^2. The fiber diameter for the mats crosslinked with the shorter PEG diacid (Mn = 250) increased to 110 ± 40 nm with an average pore size of 0.11 ± 0.04 μm^2. The mats crosslinked with the longer PEG diacid (Mn = 600) had fiber diameters of 180 ± 10 nm with an average pore size 0.01 ± 0.02 μm^2.
The objective of the experimentation was to explore the effect of crosslinker chain length on the morphology of nanofiber mats. Specifically, poly(vinyl alcohol (PVA) was electrospun into nanofiber mats and poly(ethylene) glycol bis(carboxylic acid) (PEG diacid) was used as the crosslinking agent. As-spun fibers had average fiber diameter of 70 ± 30 nm with an average pore size of 0.10 ± 0.16 μm^2. The fiber diameter for the mats crosslinked with the shorter PEG diacid (Mn = 250) increased to 110 ± 40 nm with an average pore size of 0.11 ± 0.04 μm^2. The mats crosslinked with the longer PEG diacid (Mn = 600) had fiber diameters of 180 ± 10 nm with an average pore size 0.01 ± 0.02 μm^2.
ContributorsRomero, Felicia Navidad (Author) / Green, Matthew D. (Thesis director) / Lind, Mary Laura (Committee member) / Long, Timothy E. (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
The excessive use of fossil fuels over the last few centuries has led to unprecedented changes in climate and a steady increase in the average surface global temperatures. Direct Air Capture(DAC) aims to capture CO2 directly from the atmosphere and alleviate some of the adverse effects of climate change. This dissertation focuses on methodologies to make advanced functional materials that show good potential to be used as DAC sorbents. Details on sorbent material synthesis and post-synthesis methods to obtain high surface area morphologies are described in detail. First, by incorporating K2CO3 into activated carbon (AC) fiber felts, the sorption kinetics was significantly improved by increasing the surface area of K2CO3 in contact with air. The AC-K2CO3 fiber composite felts are flexible, cheap, easy to manufacture, chemically stable, and show excellent DAC capacity and (de)sorption rates, with stable performance up to ten cycles. The best composite felts collected an average of 478 µmol of CO2 per gram of composite during 4 h of exposure to ambient (24% RH) air that had a CO2 concentration of 400-450 ppm over 10 cycles. Secondly, incorporating the amino acid L-arginine (L-Arg) into a poly(vinyl alcohol) (PVA) nanofiber support structure, created porous substrates with very high surface areas of L-Arg available for CO2 sorption. The bio-inspired PVA-Arg nanofiber composites are flexible and show excellent DAC performance compared to bulk L-Arg. The nanofiber composites are fabricated from an electrospinning process using an aqueous polymer solution. High ambient humidity levels improve sorption performance significantly. The best performing nanofiber composite collected 542 µmol of CO2 per gram of composite during 2 h of exposure to ambient, high humidity (100% RH) air that had a CO2 concentration of 400-450 ppm. Finally, poly(vinyl guanidine) (PVG) polymer was synthesized and tested for sorption performance. The fabrication of PVG nanofibers, divinyl benzene crosslinked PVG beads and glutaraldehyde crosslinked PVG were demonstrated. The sorption performance of the fabricated sorbents were tested with the glutaraldehyde crosslinked PVG having a dynamic sorption capacity of over 1 mmol of CO2 per gram of polymer in 3 h. The sorption capability of liquid PVG was also explored.
ContributorsModayil Korah, Mani (Author) / Green, Matthew D (Thesis advisor) / Lackner, Klaus (Committee member) / Long, Timothy E (Committee member) / Thomas, Marylaura L (Committee member) / Jin, Kailong (Committee member) / Arizona State University (Publisher)
Created2024
Description
ABSTRACT
Large-pore metal-organic framework (MOF) membranes offer potential in a number of gas and liquid separations due to their wide and selective adsorption capacities. A key characteristic of a number of MOF and zeolitic imidazolate framework (ZIF) membranes is their highly selective adsorption capacities for CO2. These membranes offer very tangible potential to separate CO2 in a wide array of industrially relevant separation processes, such as the separation from CO2 in flue gas emissions, as well as the sweetening of methane.
By virtue of this, the purpose of this dissertation is to synthesize and characterize two linear large-pore MOF membranes, MOF-5 and ZIF-68, and to study their gas separation properties in binary mixtures of CO¬2/N2 and CO2/CH4. The three main objectives researched are as follows. The first is to study the pervaporation behavior and stability of MOF-5; this is imperative because although MOF-5 exhibits desirable adsorption and separation characteristics, it is very unstable in atmospheric conditions. In determining its stability and behavior in pervaporation, this material can be utilized in conditions wherein atmospheric levels of moisture can be avoided. The second objective is to synthesize, optimize and characterize a linear, more stable MOF membrane, ZIF-68. The final objective is to study in tandem the high-pressure gas separation behavior of MOF-5 and ZIF-68 in binary gas systems of both CO2/N2 and CO2/CH4.
Continuous ZIF-68 membranes were synthesized via the reactive seeding method and the modified reactive seeding method. These membranes, as with the MOF-5 membranes synthesized herein, both showed adherence to Knudsen diffusion, indicating limited defects. Organic solvent experiments indicated that MOF-5 and ZIF-68 were stable in a variety of organic solvents, but both showed reductions in permeation flux of the tested molecules. These reductions were attributed to fouling and found to be cumulative up until a saturation of available bonding sites for molecules was reached and stable pervaporation permeances were reached for both. Gas separation behavior for MOF-5 showed direct dependence on the CO2 partial pressure and the overall feed pressure, while ZIF-68 did not show similar behavior. Differences in separation behavior are attributable to orientation of the ZIF-68 membranes.
Large-pore metal-organic framework (MOF) membranes offer potential in a number of gas and liquid separations due to their wide and selective adsorption capacities. A key characteristic of a number of MOF and zeolitic imidazolate framework (ZIF) membranes is their highly selective adsorption capacities for CO2. These membranes offer very tangible potential to separate CO2 in a wide array of industrially relevant separation processes, such as the separation from CO2 in flue gas emissions, as well as the sweetening of methane.
By virtue of this, the purpose of this dissertation is to synthesize and characterize two linear large-pore MOF membranes, MOF-5 and ZIF-68, and to study their gas separation properties in binary mixtures of CO¬2/N2 and CO2/CH4. The three main objectives researched are as follows. The first is to study the pervaporation behavior and stability of MOF-5; this is imperative because although MOF-5 exhibits desirable adsorption and separation characteristics, it is very unstable in atmospheric conditions. In determining its stability and behavior in pervaporation, this material can be utilized in conditions wherein atmospheric levels of moisture can be avoided. The second objective is to synthesize, optimize and characterize a linear, more stable MOF membrane, ZIF-68. The final objective is to study in tandem the high-pressure gas separation behavior of MOF-5 and ZIF-68 in binary gas systems of both CO2/N2 and CO2/CH4.
Continuous ZIF-68 membranes were synthesized via the reactive seeding method and the modified reactive seeding method. These membranes, as with the MOF-5 membranes synthesized herein, both showed adherence to Knudsen diffusion, indicating limited defects. Organic solvent experiments indicated that MOF-5 and ZIF-68 were stable in a variety of organic solvents, but both showed reductions in permeation flux of the tested molecules. These reductions were attributed to fouling and found to be cumulative up until a saturation of available bonding sites for molecules was reached and stable pervaporation permeances were reached for both. Gas separation behavior for MOF-5 showed direct dependence on the CO2 partial pressure and the overall feed pressure, while ZIF-68 did not show similar behavior. Differences in separation behavior are attributable to orientation of the ZIF-68 membranes.
ContributorsKasik, Alexandra Marie (Author) / Lin, Jerry (Thesis advisor) / Tasooji, Amaneh (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2015
Description
Zwitterionic polymers, due to their supurior capability of electrostatically induced hydration, have been considered as effective functionalities to alleviate bio-fouling of reverse osmosis (RO) membranes. Bulk modification of polysulfone-based matrices to improve hydrophilicity, on the other hand, is favored due to the high membrane performance, processibility, and intrinsic chlorine resistance. Here a novel synthetic method was demonstrated to prepare zwitterionic poly(arylene ether sulfone) (PAES) copolymers, which was blended with native polysulfone (PSf) to fabricate free-standing asymmetric membranes via non-solvent induced phase separation process. Both the porosity of the support layer and surface hydrophilicity increased drastically due to the incorporation of zwitterion functionalities in the rigid polysulfone matrix. The water permeance and antifouling ability of the blend membranes were both remarkably improved to 2.5 Lm−2 h−1 bar−1 and 94% of flux recovery ratio, respectively, while salt rejection remained at a high level (98%) even under the high exposure to chlorine (8,000 ppm•h). Besides the preliminary blended membrane design, for the future membrane property enhancement, this dissertation also focused on polymer structure optimizations via elucidating the fundamentals from two perspectives: 1). Synthetic reaction kinetics and mechanisms on polycondensation of PAES. Interestingly, in combination of experiments and the computational calculations by density functional theory (DFT) methods in this work, only the aryl chlorides (ArCl) monomer follows the classical second-order reaction kinetics of aromatic nucleophilic substitution (SNAr) mechanism, while the kinetics of the aryl fluorides (ArF) reaction fit a third-order rate law. The third order reaction behavior of the ArF monomer is attributed to the activation of the carbon-fluorine bond by two potassium cations (at least one bounded to phenolate), which associate as a strong three-body complex. This complex acts as the predominant reactant during the attack by the nucleophile. 2). Optimized copolymer structures were developed for controlled high molecular weight (Mw ~ 65 kDa) and zwitterionic charge content (0~100 mol%), via off-set stoichiometry during polycondensations, following with thiol-ene click reaction and ring-opening of sultone to introduce the sulfobetaine functional groups. The structure-property-morphology relationships were elucidated for better understanding atomic-level features in the charged polymers for future high-performance desalination applications.
ContributorsYang, Yi, Ph.D (Author) / Green, Matthew D (Thesis advisor) / Lin, Jerry Y.S. (Committee member) / Lind, Marylaura (Committee member) / Perreault, Francois (Committee member) / Deng, Shuguang (Committee member) / Arizona State University (Publisher)
Created2019