Matching Items (16)
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- All Subjects: energy
- All Subjects: Zeolites
- Creators: Chemical Engineering Program
Description
Solid oxide fuel cells have become a promising candidate in the development of high-density clean energy sources for the rapidly increasing demands in energy and global sustainability. In order to understand more about solid oxide fuel cells, the important step is to understand how to model heterogeneous materials. Heterogeneous materials are abundant in nature and also created in various processes. The diverse properties exhibited by these materials result from their complex microstructures, which also make it hard to model the material. Microstructure modeling and reconstruction on a meso-scale level is needed in order to produce heterogeneous models without having to shave and image every slice of the physical material, which is a destructive and irreversible process. Yeong and Torquato [1] introduced a stochastic optimization technique that enables the generation of a model of the material with the use of correlation functions. Spatial correlation functions of each of the various phases within the heterogeneous structure are collected from a two-dimensional micrograph representing a slice of a solid oxide fuel cell through computational means. The assumption is that two-dimensional images contain key structural information representative of the associated full three-dimensional microstructure. The collected spatial correlation functions, a combination of one-point and two-point correlation functions are then outputted and are representative of the material. In the reconstruction process, the characteristic two-point correlation functions is then inputted through a series of computational modeling codes and software to generate a three-dimensional visual model that is statistically similar to that of the original two-dimensional micrograph. Furthermore, parameters of temperature cooling stages and number of pixel exchanges per temperature stage are utilized and altered accordingly to observe which parameters has a higher impact on the reconstruction results. Stochastic optimization techniques to produce three-dimensional visual models from two-dimensional micrographs are therefore a statistically reliable method to understanding heterogeneous materials.
ContributorsPhan, Richard Dylan (Author) / Jiao, Yang (Thesis director) / Ren, Yi (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Due to the environmental problems caused by global warming, it has become necessary to reduce greenhouse gas emissions across the planet. Biofuels, such as ethanol, have proven to release cleaner emissions when combusted. However, large scale production of these alcohols is uneconomical and inefficient due to limitations in standard separation processes, the most common being distillation. Pervaporation is a novel separation technique that utilizes a specialized membrane to separate multicomponent solutions. In this research project, pervaporation utilizing ZIF-71/PDMS mixed matrix membranes are investigated to see their ability to recover ethanol from an ethanol/aqueous separation. Membranes with varying nanoparticle concentrations were created and their performances were analyzed. While the final results indicate that no correlation exists between nanoparticle weight percentage and selectivity, this technology is still a promising avenue for biofuel production. Future work will be conducted to improve this existing process and enhance membrane selectivity.
ContributorsHoward, Chelsea Elizabeth (Author) / Lind, Mary Laura (Thesis director) / Nielsen, David (Committee member) / Greenlee, Lauren (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor) / Materials Science and Engineering Program (Contributor)
Created2015-05
Description
Carbon capture is an essential way to reduce greenhouse gas emissions. One way to decrease the emissions is through the use of adsorbents such as zeolites. Dr. Dong-Kyun Seo’s group (School of Molecular Sciences, Arizona State University) synthesized the nanostructured faujasite (NaX). The zeolite was characterized using Scanning Electron Microscopy (SEM) and the physisorption properties were determined using ASAP 2020. ASAP 2020 tests of the nano-zeolite pellets at 77K in a liquid N2 bath determined the BET surface area of 547.1 m2/mol, T-plot micropore volume of 0.2257 cm3/g, and an adsorption average pore width of 5.9 Å. The adsorption isotherm (equilibrium) of CH4, N2, and CO2 were measured at 25ºC. Adsorption isotherm experiments concluded that the linear isotherm was the best fit for N2, and CH4 and the Sips isotherm was a better fit than the Langmuir and Freundlich isotherm for CO2. At 25ºC and 1 atm the zeolite capacity for CO2 is 4.3339 mmol/g, 0.1948 mmol/g for CH4, and 0.3534 mmol/g for N2. The zeolite has a higher CO2 capacity than the conventional NaX zeolite. Breakthrough experiments were performed in a fixed bed 22in, 0.5 in packing height and width at 1 atm and 298 K with nano-zeolite pellets. The gas chromatographer tested and recorded the data every two minutes with a flow rate of 10 cm3/min for N2 and 10 cm3/min CO2. Breakthrough simulations of the zeolite in a fixed bed adsorber column were conducted on MATLAB utilizing varying pressures, flow rates, and fed ratios of various CO2, N2 and CH4. Simulations using ideal adsorbed solution theory (IAST) calculations determined that the selectivity of CO2 in flue gas (15% CO2 + 85% N2) is 571.79 at 1 MPa, significantly higher than commercial zeolites and literature. The nanostructured faujasite zeolite appears to be a very promising adsorbent for CO2/N2 capture from flue gas and the separation of CO2/N2.
ContributorsClark, Krysta D. (Author) / Deng, Shuguang (Thesis director) / Green, Matthew (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
The recovery of biofuels permits renewable alternatives to present day fossil fuels that cause devastating effects on the planet. Pervaporation is a separation process that shows promise for the separation of ethanol from biologically fermentation broths. The performance of thin film composite membranes of polydimethylsiloxane (PDMS) and zeolite imidazolate frameworks (ZIF-71) dip coated onto a porous substrate are analyzed. Pervaporation performance factors of flux, separation factor and selectivity are measured for varying ZIF-71 loadings of pure PDMS, 5 wt%, 12.5 wt% and 25 wt% at 60 oC with a 2 wt% ethanol/water feed. The increase in ZIF-71 loadings increased the performance of PDMS to produce higher flux, higher separation factor and high selectivity than pure polymeric films.
ContributorsLau, Ching Yan (Author) / Lind, Mary Laura (Thesis director) / Durgun, Pinar Cay (Committee member) / Lively, Ryan (Committee member) / Barrett, The Honors College (Contributor) / School of International Letters and Cultures (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05
Description
Currently, approximately 40% of the world’s electricity is generated from coal and coal power plants are one of the major sources of greenhouse gases accounting for a third of all CO2 emissions. The Integrated Gasification Combined Cycle (IGCC) has been shown to provide an increase in plant efficiency compared to traditional coal-based power generation processes resulting in a reduction of greenhouse gas emissions. The goal of this project was to analyze the performance of a new SNDC ceramic-carbonate dual-phase membrane for CO2 separation. The chemical formula for the SNDC-carbonate membrane was Sm0.075Nd0.075Ce0.85O1.925. This project also focused on the use of this membrane for pre-combustion CO2 capture coupled with a water gas shift (WGS) reaction for a 1000 MW power plant. The addition of this membrane to the traditional IGCC process provides a purer H2 stream for combustion in the gas turbine and results in lower operating costs and increased efficiencies for the plant. At 900 °C the CO2 flux and permeance of the SNDC-carbonate membrane were 0.65 mL/cm2•min and 1.0×10-7 mol/m2•s•Pa, respectively. Detailed in this report are the following: background regarding CO2 separation membranes and IGCC power plants, SNDC tubular membrane preparation and characterization, IGCC with membrane reactor plant design, process heat and mass balance, and plant cost estimations.
ContributorsDunteman, Nicholas Powell (Author) / Lin, Jerry (Thesis director) / Dong, Xueliang (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor) / School of Sustainability (Contributor)
Created2014-05
Description
The two central goals of this project were 1) to develop a testing method utilizing coatings on ultra-thin stainless steel to measure the thermal conductivity (k) of battery electrode materials and composites, and 2) to measure and compare the thermal conductivities of lithium iron phosphate (LiFePO4, "LFP") in industry-standard graphite/LFP mixtures as well as graphene/LFP mixtures and a synthesized graphene/LFP nanocomposite. Graphene synthesis was attempted before purchasing graphene materials, and further exploration of graphene synthesis is recommended due to limitations in purchased product quality. While it was determined after extensive experimentation that the graphene/LFP nanocomposite could not be successfully synthesized according to current literature information, a mixed composite of graphene/LFP was successfully tested and found to have k = 0.23 W/m*K. This result provides a starting point for further thermal testing method development and k optimization in Li-ion battery electrode nanocomposites.
ContributorsStehlik, Daniel Wesley (Author) / Chan, Candace K. (Thesis director) / Dai, Lenore (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05
Description
In microbial fuel cells (MFCs) the biocathode is developed as a potential alternative to chemical cathodic catalysts, which are deemed as expensive and unsustainable for applications. These cells utilize different types of microorganisms as catalysts to promote biodegradation of organic matter while simultaneously converting energy released in metabolic reactions into electrical energy. Most current research have focused more on the anodic microbes, including the current generating bacteria species, anodic microbial community composition, and the mechanisms of the extracellular electron transfer. Compared to the anode, research on the microbes of the biocathode of the MFCs are very limited and are heavily focused on the role of the bacteria in the system. Thus, further understand of the mechanism of the microbial community in the biocathode will create new engineering applications for sustainable energy. Previous research conducted by Strycharz-Glaven et al. presented an electrochemical analysis of a Marinobacter-dominated biocathode communitygrown on biocathodes in sediment/seawater-based MFCs. Chronoamperometry results indicated that current densities up to -0.04 A/m2 were produced for the biocathode. Cyclic voltammetry responses indicated a midpoint potential at 0.196 V ± 0.01 V. However, the reactor design for these experiments showed that no oxygen is supplied to the electrochemical system. By incorporating an air diffusion membrane to the cathode of the reactor, chronoamperometry results have produced current density in the system up to -0.15 A/m2. Cyclic voltammetry results have also displayed a midpoint potential of 0.25 V ± 0.01 V under scan rates of 0.2 mV/s. Thus, this electrochemical setup has increased the current output of the system.
ContributorsWang, Zixuan (Author) / Torres, Cesar (Thesis director) / Hart, Steven (Committee member) / Materials Science and Engineering Program (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
This honors thesis is focused on two separate catalysis projects conducted under the mentorship of Dr. Javier Pérez-Ramírez at ETH Zürich. The first project explored ethylene oxychlorination over supported europium oxychloride catalysts. The second project investigated alkyne semihydrogenation over nickel phosphide catalysts. This work is the subject of a publication of which I am a co-author, as cited below.
Project 1 Abstract: Ethylene Oxychlorination
The current two-step process for the industrial process of vinyl chloride production involves CuCl2 catalyzed ethylene oxychlorination to ethylene dichloride followed by thermal cracking of the latter to vinyl chloride. To date, no industrial application of a one-step process is available. To close this gap, this work evaluates a wide range of self-prepared supported CeO2 and EuOCl catalysts for one-step production of vinyl chloride from ethylene in a fixed-bed reactor at 623 773 K and 1 bar using feed ratios of C2H4:HCl:O2:Ar:He = 3:3 6:1.5 6:3:82 89.5. Among all studied systems, CeO2/ZrO2 and CeO2/Zeolite MS show the highest activity but suffer from severe combustion of ethylene, forming COx, while 20 wt.% EuOCl/γ-Al2O3 leads to the best vinyl chloride selectivity of 87% at 15.6% C2H4 conversion with complete suppression of CO2 formation and only 4% selectivity to CO conversion for over 100 h on stream. Characterization by XRD and EDX mapping reveals that much of the Eu is present in non-active phases such as Al2Eu or EuAl4, indicating that alternative synthesis methods could be employed to better utilize the metal. A linear relationship between conversion and metal loading is found for this catalyst, indicating that always part of the used Eu is available as EuOCl, while the rest forms inactive europium aluminate species. Zeolite-supported EuOCl slightly outperforms EuOCl/γ Al2O3 in terms of total yield, but is prone to significant coking and is unstable. Even though a lot of Eu seems locked in inactive species on EuOCl/γ Al2O3, these results indicate possible savings of nearly 16,000 USD per kg of catalyst compared to a bulk EuOCl catalyst. These very promising findings constitute a crucial step for process intensification of polyvinyl chloride production and exploring the potential of supported EuOCl catalysts in industrially-relevant reactions.
Project 2 Abstract: Alkyne Semihydrogenation
Despite strongly suffering from poor noble metal utilization and a highly toxic selectivity modifier (Pb), the archetypal catalyst applied for the three-phase alkyne semihydrogenation, the Pb-doped Pd/CaCO3 (Lindlar catalyst), is still being utilized at industrial level. Inspired by the very recent strategies involving the modification of Pd with p-block elements (i.e., S), this work extrapolates the concept by preparing crystalline metal phosphides with controlled stoichiometry. To develop an affordable and environmentally-friendly alternative to traditional hydrogenation catalysts, nickel, a metal belonging to the same group as Pd and capable of splitting molecular hydrogen has been selected. Herein, a simple two-step synthesis procedure involving nontoxic precursors was used to synthesize bulk nickel phosphides with different stoichiometries (Ni2P, Ni5P4, and Ni12P5) by controlling the P:Ni ratios. To uncover structural and surface features, this catalyst family is characterized with an array of methods including X-ray diffraction (XRD), 31P magic-angle nuclear magnetic resonance (MAS-NMR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Bulk-sensitive techniques prove the successful preparation of pure phases while XPS analysis unravels the facile passivation occurring at the NixPy surface that persists even after reductive treatment. To assess the characteristic surface fingerprints of these materials, Ar sputtering was carried out at different penetration depths, reveling the presence of Ni+ and P-species. Continuous-flow three-phase hydrogenations of short-chain acetylenic compounds display that the oxidized layer covering the surface is reduced under reaction conditions, as evidenced by the induction period before reaching the steady state performance. To assess the impact of the phosphidation treatment on catalytic performance, the catalysts were benchmarked against a commercial Ni/SiO2-Al2O3 sample. While Ni/SiO2-Al2O3 presents very low selectivity to the alkene (the selectivity is about 10% at full conversion) attributed to the well-known tendency of naked nickel nanoparticles to form hydrides, the performance of nickel phosphides is highly selective and independent of P:Ni ratio. In line with previous findings on PdxS, kinetic tests indicate the occurrence of a dual-site mechanism where the alkyne and hydrogen do not compete for the same site.
This work is the subject of a publication of which I am a co-author, as cited below.
D. Albani; K. Karajovic; B. Tata; Q. Li; S. Mitchell; N. López; J. Pérez-Ramírez. Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation. ChemCatChem 2019. doi.org/10.1002/cctc.201801430
Project 1 Abstract: Ethylene Oxychlorination
The current two-step process for the industrial process of vinyl chloride production involves CuCl2 catalyzed ethylene oxychlorination to ethylene dichloride followed by thermal cracking of the latter to vinyl chloride. To date, no industrial application of a one-step process is available. To close this gap, this work evaluates a wide range of self-prepared supported CeO2 and EuOCl catalysts for one-step production of vinyl chloride from ethylene in a fixed-bed reactor at 623 773 K and 1 bar using feed ratios of C2H4:HCl:O2:Ar:He = 3:3 6:1.5 6:3:82 89.5. Among all studied systems, CeO2/ZrO2 and CeO2/Zeolite MS show the highest activity but suffer from severe combustion of ethylene, forming COx, while 20 wt.% EuOCl/γ-Al2O3 leads to the best vinyl chloride selectivity of 87% at 15.6% C2H4 conversion with complete suppression of CO2 formation and only 4% selectivity to CO conversion for over 100 h on stream. Characterization by XRD and EDX mapping reveals that much of the Eu is present in non-active phases such as Al2Eu or EuAl4, indicating that alternative synthesis methods could be employed to better utilize the metal. A linear relationship between conversion and metal loading is found for this catalyst, indicating that always part of the used Eu is available as EuOCl, while the rest forms inactive europium aluminate species. Zeolite-supported EuOCl slightly outperforms EuOCl/γ Al2O3 in terms of total yield, but is prone to significant coking and is unstable. Even though a lot of Eu seems locked in inactive species on EuOCl/γ Al2O3, these results indicate possible savings of nearly 16,000 USD per kg of catalyst compared to a bulk EuOCl catalyst. These very promising findings constitute a crucial step for process intensification of polyvinyl chloride production and exploring the potential of supported EuOCl catalysts in industrially-relevant reactions.
Project 2 Abstract: Alkyne Semihydrogenation
Despite strongly suffering from poor noble metal utilization and a highly toxic selectivity modifier (Pb), the archetypal catalyst applied for the three-phase alkyne semihydrogenation, the Pb-doped Pd/CaCO3 (Lindlar catalyst), is still being utilized at industrial level. Inspired by the very recent strategies involving the modification of Pd with p-block elements (i.e., S), this work extrapolates the concept by preparing crystalline metal phosphides with controlled stoichiometry. To develop an affordable and environmentally-friendly alternative to traditional hydrogenation catalysts, nickel, a metal belonging to the same group as Pd and capable of splitting molecular hydrogen has been selected. Herein, a simple two-step synthesis procedure involving nontoxic precursors was used to synthesize bulk nickel phosphides with different stoichiometries (Ni2P, Ni5P4, and Ni12P5) by controlling the P:Ni ratios. To uncover structural and surface features, this catalyst family is characterized with an array of methods including X-ray diffraction (XRD), 31P magic-angle nuclear magnetic resonance (MAS-NMR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Bulk-sensitive techniques prove the successful preparation of pure phases while XPS analysis unravels the facile passivation occurring at the NixPy surface that persists even after reductive treatment. To assess the characteristic surface fingerprints of these materials, Ar sputtering was carried out at different penetration depths, reveling the presence of Ni+ and P-species. Continuous-flow three-phase hydrogenations of short-chain acetylenic compounds display that the oxidized layer covering the surface is reduced under reaction conditions, as evidenced by the induction period before reaching the steady state performance. To assess the impact of the phosphidation treatment on catalytic performance, the catalysts were benchmarked against a commercial Ni/SiO2-Al2O3 sample. While Ni/SiO2-Al2O3 presents very low selectivity to the alkene (the selectivity is about 10% at full conversion) attributed to the well-known tendency of naked nickel nanoparticles to form hydrides, the performance of nickel phosphides is highly selective and independent of P:Ni ratio. In line with previous findings on PdxS, kinetic tests indicate the occurrence of a dual-site mechanism where the alkyne and hydrogen do not compete for the same site.
This work is the subject of a publication of which I am a co-author, as cited below.
D. Albani; K. Karajovic; B. Tata; Q. Li; S. Mitchell; N. López; J. Pérez-Ramírez. Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation. ChemCatChem 2019. doi.org/10.1002/cctc.201801430
ContributorsTata, Bharath (Author) / Deng, Shuguang (Thesis director) / Muhich, Christopher (Committee member) / Chemical Engineering Program (Contributor, Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05
Description
Even though access to purified water has improved, there are still many people and locations that do not have this convenience. Approximately 1.2 billion people lack access to safe drinking water and 2.6 billion people have little or no sanitation. Furthermore, breakthroughs in water purification technology are essential to combat these issues. While there are several approaches to water purification, membrane processes are widely used based on their numerous advantages, including high operating temperature and low energy input. In essence, membranes do not require chemical additives, thermal inputs, or regeneration of spent media. The spin coating procedure was used to make a total of 94 membrane samples by adjusting the following variables: membrane support, membrane wetting, solvent, polyacrylonitrile (PAN) content, water contant, Linde Type A (LTA) zeolite content, and the rotations per minute (RPM) of the spin coater. Parameters that were held constant include PAN for the permeable dispersion layer, LTA zeolites as the inorganic filler material, and a spin time of 30 seconds for the spin coater. There were key findings in both the preliminary and core data sets. From the preliminary membrane samples 1 \u2014 40, a baseline was established to use for the core data: polysulfone (PSf) support, 1 \u2014 3% PAN content, and 1 \u2014 3% LTA zeolite content. Flux analysis revealed many inconsistencies in groups 1 \u2014 13 such as unreasonably high error bars (+50%), flow rates that were near zero or extremely high (+15,000 L hr-1 m-2), and lack of a clear trend for membrane specifications. Membranes with a high degree of polymer \u2014 zeolite aggregation on the surface had very low flux values. A higher flux of 4,700 L hr-1 m-2 was correlated to gap and hole formation on the membrane surface. It was shown in group 7 that an increasing degree of surface defects corresponded to an increasing flux of 17,000 L hr-1 m-2. Although the target flux for a defect \u2014 free membrane lies between 500 \u2014 4,000 L hr-1 m-2, there were not any groups with flux values in this range. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) analysis revealed that the observed group similarities could not be attributed to individual membrane specifications. However, this data showed chemical fingerprint overlap across all groups, which were synthesized with varying quantities of the same chemicals. Analysis of flux data, SEM images, and ATR-FTIR data all suggest that the spin coating procedure leads to inconsistent results. Although the spin coater provides flexibility in user control, its advantages are outweighed by the limited control of surface uniformity, zeolite dispersion, and defect formation. It has been shown that the spin coating process is not compatible with the formation of a uniform polymer \u2014 zeolite layer in these experiments.
ContributorsMaltagliati, Alexander Justin (Author) / Lind, Mary Laura (Thesis director) / Durgun, Pinar Cay (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
Description
One of the grand challenges of engineering is to provide access to clean water because it is predicted that by 2025 more than two thirds of the world’s population will face severe water shortages. To combat this global issue, our lab focuses on creating a novel composite membrane to recover potable water from waste. For use as the water-selective component in this membrane design Linde Type A zeolites were synthesized for optimal size without the use of a template. Current template-free synthesis of zeolite LTA produces particles that are too large for our application therefore the particle size was reduced in this study to reduce fouling of the membrane while also investigating the nanoparticle synthesis mechanisms. The time and temperature of the reaction and the aging of the precursor gel were systematically modified and observed to determine the optimal conditions for producing the particles. Scanning electron microscopy, x-ray diffraction, and energy dispersive x-ray analysis were used for characterization. Sub-micron sized particles were synthesized at 2 weeks aging time at -8°C with an average size of 0.6 micrometers, a size suitable for our membrane. There is a limit to the posterity and uniformity of particles produced from modifying the reaction time and temperature. All results follow general crystallization theory. Longer aging produced smaller particles, consistent with nucleation theory. Spinodal decomposition is predicted to affect nucleation clustering during aging due to the temperature scheme. Efforts will be made to shorten the effective aging time and these particles will eventually be incorporated into our mixed matrix osmosis membrane.
ContributorsKing, Julia Ann (Author) / Lind, Mary Laura (Thesis director) / Durgun, Pinar Cay (Committee member) / Chemical Engineering Program (Contributor) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05