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- All Subjects: chemical engineering
- Creators: Chemical Engineering Program
- Status: Published
Description
This study aims to provide a foundation for future work on photo-responsive polymer composite materials to be utilized in additive manufacturing processes. The curing rate of 2,2-dimethoxy-2-phenyl-acetophenone (DMPA) in thin (<20 µm) and thick (>2 mm) layers of DMPA and poly(ethylene glycol) diacrylate (PEG-DA) mixtures was assessed for 5.0 w/v% (grams per 100 mL) concentrations of DMPA dissolved in PEG-DA. The polymerization rate and quality of curing was found to decrease as the concentration of DMPA increased beyond 1.0 w/v%; thus, confirming the existence of an optimum photo-initiator concentration for a specific sheet thickness. The optimum photo-initiator concentration for a 3-3.1 mm thick sheet of PEG-DA microstructure was determined to be between 0.3 and 0.38 w/v% DMPA. The addition of 1,6-hexanediol or 1,3-butanediol to the optimum photo-initiator concentrated solution of DMPA and PEG-DA was found to increase the Tg of the samples; however, the samples could not fully cure within 40-50 s, which suggested a decrease in polymerization rate. Lastly, the DMPA photo-initiator does not produce gaseous byproducts and is translucent when fully cured, which makes it attractive for infusion with strengthening materials because quality light penetration is paramount to quick polymerization rates. It is recommended that more trials be conducted to evaluate the mechanical properties of the optimum curing rate for DMPA and PEG-DA microstructures as well as a mechanical property comparison following the addition of either of the two alcohols.
ContributorsPiper, Tyler Irvin (Author) / Green, Green (Thesis director) / Lind, Mary Laura (Committee member) / School of Sustainability (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
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
This study aims to determine the feasibility of producing mechanophore-incorporated epoxy that can be healed. This was accomplished by grafting a synthesized mechanophore into tris(2-aminoethyl)amine to create a new epoxy hardener. Then this branched hardener was combined with a second hardener, diethylenetriamine (DETA). A proper ratio of the branched hardener to the DETA will ensure that the created epoxy will retain the force responsive characteristics without a noticeable decline in both the physical and thermal properties. Furthermore, it was desired that the natural structure of the epoxy would be left in place, and there would only be enough branched hardener present to elicit a force response and provide the possibility for healing. The two hardeners would then be added to Diglycidyl Ether of Bisphenol F (DGEBPF), which is the epoxy resin. The mechanophore-incorporated epoxy was compared to a standard epoxy—just DETA and DGEBPF—and it was determined that the incorporation of the mechanophore led to an 8.2 degrees Celsius increase in glass transition temperature, and a 33.0% increase in cross link density. This justified the mechanophore-incorporated epoxy as a feasible alternative to the standard, as its primary thermal and physical properties were not only equal, but superior. Then samples of the mechanophore-incorporated epoxy were damaged with a 3% tensile strain. This would cause a cycloreversion in the central cyclobutane inside of the mechanophore. Then they were healed with UV light, which would redimerize the severed hardener moieties. The healed samples saw a 4.69% increase in cross-link density, demonstrating that healing was occurring.
ContributorsPauley, Bradley (Author) / Dai, Lenore (Thesis director) / Gunckel, Ryan (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-12
Description
This report investigates the effects of autolyzing, fermentation medium, fermentation temperature, and proofing medium on the growth and porosity of 50% whole wheat sourdough bread. A model was designed using a 24 statistical design of experiment with replicates to screen and quantify the individual and combined effects of the aforementioned factors on the area of a 1 cm cross-sectional cut from each loaf. Fermentation temperature had the single largest effect, with colder fermented loaves being on average 10 cm2 larger than their warmer fermented counter parts. Autolyzing had little individual effect, but the strengthened gluten network abated some of the degassing and overproofing that is a consequent handling the dough or letting it ferment too much. This investigation quantifies how to maximize gluten development and yeast growth to create the airiest whole wheat sourdough, a healthier and easier to digest bread than many commercially available.
ContributorsLay, Michael Loren (Author) / Emady, Heather (Thesis director) / Adepu, Manogna (Committee member) / School of Sustainability (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
Layered double hydroxides (LDHs), also known as hydrotalcite-like materials, are extensively used as precursors for the preparation of (photo-)catalysts, electrodes, magnetic materials, sorbents, etc. The synthesis typically involves the transformation to the corresponding mixed metal oxide via calcination, resulting in atomically dispersed mixed metal oxides (MMOs). This process alters the porosity of the materials, with crucial implications for the performance in many applications. Yet, the mechanisms of pore formation and collapse are poorly understood. Combining an integrated in situ and ex situ characterization approach, here we follow the evolution of porosity changes during the thermal decomposition of LDHs integrating different divalent (Mg, Ni) and trivalent (Al, Ga) metals. Variations in porous properties determined by high-resolution argon sorption are linked to the morphological and compositional changes in the samples by in situ transmission electron microscopy coupled with energy dispersive X-ray spectroscopy, which is facilitated by the synthesis of well crystallized LDHs of large crystal size. The observations are correlated with the phase changes identified by X-ray diffraction, the mass losses evidenced by thermogravimetric analysis, the structural changes determined by infrared and nuclear magnetic resonance spectroscopy, and the pore connectivity analyzed by positron annihilation spectroscopy. The findings show that the multimetallic nature of the LDH governs the size and distribution (geometry, location, and connectivity) of the mesopores developed, which is controlled by the crystallization of the MMO phase, providing key insights for the improved design of porous mixed metal oxides.
ContributorsMurty, Rohan Aditya (Author) / Deng, Shuguang (Thesis director) / Nielsen, David R. (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2017-05
Description
As global population and demand for electrical power increase, humanity is faced with the growing challenge of harnessing and distributing enough energy to sustain the developing world. Currently, fossil fuels (coal
atural gas) are our main sources of electricity. However, their cost is increasing, they are nonrenewable, and they are very harmful to the environment. Thus, capacity expansion in the renewable energy sector must be realized to offset higher energy demand and reduce dependence on fossil fuels. Solar energy represents a practical solution, as installed global solar capacity has been increasing exponentially over the past 2 decades. However, even with government incentives, solar energy price ($/kWh) continues to be highly dependent on political climate and raw material (silicon and silver) cost. To realistically and cost effectively meet the projected expansions within the solar industry, silver must be replaced with less costly and more abundant metals (such as copper) in the front-grid metallization process of photovoltaic cells. Copper, while offering both higher achievable efficiencies and a raw material cost nearly 100 times cheaper than silver, has inherent disadvantages. Specifically, copper diffuses rapidly into the silicon substrate, requires more complex and error-prone processing steps, and tends to have less adhesive strength, reducing panel robustness. In this study, nickel deposition via sputtering was analyzed, as well as overall potential of nickel as a seed layer for copper plating, which also provides a barrier layer to copper diffusion in silicon. Thermally-formed nickel silicide also reduces contact resistivity, increasing cell efficiency. It was found that at 400 \u00B0C, ideal nickel silicide formation occurred. By computer modeling, contact resistivity was found to have a significant impact on cell efficiency (up to 1.8%). Finally, sputtering proved useful to analyze nickel silicide formation, but costs and time requirements prevent it from being a practical industrial-scale metallization method.
atural gas) are our main sources of electricity. However, their cost is increasing, they are nonrenewable, and they are very harmful to the environment. Thus, capacity expansion in the renewable energy sector must be realized to offset higher energy demand and reduce dependence on fossil fuels. Solar energy represents a practical solution, as installed global solar capacity has been increasing exponentially over the past 2 decades. However, even with government incentives, solar energy price ($/kWh) continues to be highly dependent on political climate and raw material (silicon and silver) cost. To realistically and cost effectively meet the projected expansions within the solar industry, silver must be replaced with less costly and more abundant metals (such as copper) in the front-grid metallization process of photovoltaic cells. Copper, while offering both higher achievable efficiencies and a raw material cost nearly 100 times cheaper than silver, has inherent disadvantages. Specifically, copper diffuses rapidly into the silicon substrate, requires more complex and error-prone processing steps, and tends to have less adhesive strength, reducing panel robustness. In this study, nickel deposition via sputtering was analyzed, as well as overall potential of nickel as a seed layer for copper plating, which also provides a barrier layer to copper diffusion in silicon. Thermally-formed nickel silicide also reduces contact resistivity, increasing cell efficiency. It was found that at 400 \u00B0C, ideal nickel silicide formation occurred. By computer modeling, contact resistivity was found to have a significant impact on cell efficiency (up to 1.8%). Finally, sputtering proved useful to analyze nickel silicide formation, but costs and time requirements prevent it from being a practical industrial-scale metallization method.
ContributorsBliss, Lyle Brewster (Author) / Bowden, Stuart (Thesis director) / Karas, Joseph (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2017-05
Description
Anaerobic digestion (AD), a common process in wastewater treatment plants, is traditionally assessed with Biochemical Methane Potential (BMP) tests. Hydrolysis is considered its rate-limiting step. During my research, I assessed the impact of pretreatment on BMPs and microbial electrochemical cells (MECs). In the first set of experiments, BMP tests were performed using alkaline and thermal pretreated waste activated sludge (WAS), a control group, and a negative control group as samples and AD sludge (ADS) as inoculum. The data obtained suggested that BMPs do not necessarily require ADS, since samples without inoculum produced 5-20% more CH4. However, ADS appears to reduce the initial methanogenesis lag in BMPs, as no pH inhibition and immediate CH4 production were observed. Consumption rate constants, which are related to hydrolysis, were calculated using three methods based on CH4 production, SSCOD concentration, and the sum of both, called the lumped parameter. All the values observed were within literature values, yet each provide a different picture of what is happening in the system. For the second set of experiments, the current production of 3 H-type MECs were compared to the CH4 production of BMPs to assess WAS solids' biodegradability and consumption rates relative to the pretreatment methods employed for their substrate. BMPs fed with pretreated and control WAS solids were performed at 0.42 and 1.42 WAS-to-ADS ratios. An initial CH4 production lag of about 12 days was observed in the BMP assays, but MECs immediately began producing current. When compared in terms of COD, MECs produced more current than the BMPs produced CH4, indicating that the MEC may be capable of consuming different types of substrate and potentially overestimating CH4 production in anaerobic digesters. I also observed 2 to 3 different consumption events in MECs versus 3 for BMP assays, but these had similar magnitudes, durations, and starting times in the control and thermal pretreated WAS-fed assays and not in alkaline assays. This might indicate that MECs identified the differences of alkaline pretreatment, but not between control WAS and thermal pretreated WAS. Furthermore, HPLC results suggest at least one hydrolysis event, as valerate, butyrate, and traces of acetate are observed in the reactors' effluents. Moreover, a possible inhibition of valerate-fixing microbial communities due to pretreatment and the impossibility of valerate consumption by ARB might explain its presence in the reactors' effluents.
ContributorsBrown Munoz, Francisco (Author) / Torres, Cesar (Thesis director) / Rittmann, Bruce E. (Committee member) / Chemical Engineering Program (Contributor, Contributor) / Barrett, The Honors College (Contributor)
Created2017-05
Description
Rotary drums are commonly used for their high heat and mass transfer rates in the manufacture of pharmaceuticals, cement, food, and other particulate products. These processes are difficult to model because the particulate behavior is governed by the process conditions such as particle size, particle size distribution, shape, composition, and operating parameters, such as fill level and rotation rate. More research on heat transfer in rotary drums will increase operating efficiency, leading to tremendous energy savings on a global scale. This study investigates the effects of drum fill level and rotation rate on the steady-state average particle bed temperature. 3 mm silica beads and a stainless steel rotary drum were used at fill levels ranging from 10 \u2014 25 % and rotation rates from 2 \u2014 10 rpm. Four heat guns were used to heat the system via conduction and convection, and an infrared camera was used to record temperature data. A three-level, two-factor, full-factorial design of experiments was employed to determine the effects of each factor on the steady-state average bed temperature. Low fill level and high rotation rate resulted in higher steady-state average bed temperatures. A quantitative model showed that rotation rate had a larger impact on the steady-state bed temperature than fill level.
ContributorsBoepple, Brandon Richard (Author) / Emady, Heather (Thesis director) / Adepu, Manogna (Committee member) / W.P. Carey School of Business (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
The following paper discusses the potential for Designed Ankyrin Repeat Proteins (DARPin) use as a diagnostic tool for neurodegenerative diseases in particular Alzheimer's disease (AD) and Parkinson's disease (PD). The two structures investigated for AD and PD were ADC7 and PDC1. Plasmid transformation was performed in order to grow the DARPin in E. coli for simple expression. Following growth and purification the proteins were validated using SDS-PAGE, Western Blot, BCA and indirect sandwich ELISA using transgenic mouse brain tissue. Targeted functionality of the DARPin structure was utilized during characterization methods to ensure the efficacy of the protein as a diagnostic for the respective disease targets. Both the ADC7 and PDC1 demonstrated improved binding with transgenic mice compared to wild type with a maximum 1.8 and 1.7 relative ratio, respectively. Additionally, both of the proteins demonstrated exclusive binding to their disease target and did not provide false positive results.
ContributorsTindell, John (Co-author) / Card, Emma (Co-author) / Sierks, Michael (Thesis director) / Nannenga, Brent (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
Description
Arson and intentional fires account for significant property losses and over 400 civilian deaths yearly in the United States. However, clearance rates for arson offenses remain low relative to other crimes. This issue can be attributed in part to the challenges associated with performing an arson investigation, in particular the collection and interpretation of reliable data. PLOT-cryoadsorption, a dynamic headspace sampling technique developed at the National Institute of Standards and Technology, was proposed as an alternate technique for extracting ignitable liquid residues for analysis. The method was generally shown to be robust, flexible, precise, and accurate for a variety of applications. The possibility of using a real-time in situ monitor for screening samples was also discussed. This work, conducted by an undergraduate researcher, has implications in educational curricula as well as in the field of forensic science.
ContributorsNichols, Jessica Ellen (Author) / Forzani, Erica (Thesis director) / Nielsen, David (Committee member) / Tsow, Francis (Committee member) / Barrett, The Honors College (Contributor) / School of Mathematical and Statistical Sciences (Contributor) / Chemical Engineering Program (Contributor)
Created2013-05