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- Creators: Mechanical and Aerospace Engineering Program
- Creators: Muhich, Christopher
- Member of: Barrett, The Honors College Thesis/Creative Project Collection
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
It was predicted that increasing the surface area roughness would increase the number of electrons present in the reduction oxidation reaction and decrease the activation resistance of the thermogalvanic system. Decreasing the activation resistance, a component of total internal resistance, would therefore increase the power output of the cell by a small magnitude. The results showed that changing the surface area roughness of the Copper electrodes evidently had no effect on the outputs of the cell system. Additionally, the Seebeck coefficient was also unaffected by the presence of increased surface area roughness.
The work presented in the following paper is part of a continuing effort to better understand the performance of thermogalvanic cells and their heat to electrical energy transfer properties.
This work summarizes the development of a dynamic measurement platform in a cryostat to measure sample temperature response to space-like conditions and the creation a MATLAB theoretical model to predict sample temperature responses in the platform itself. An interesting variable-emittance sample called a Fabry-Perot emitter was studied for its thermal homeostasis behavior using the two developments. Using the measurement platform, it was shown that there was no thermal homeostatic behavior demonstrated by the sample at steady state temperatures. Theoretical calculations show other ways to demonstrate the cooling homeostasis behavior through time-varying heat inputs. Factors within the system such as heat loss and thermal mass contributed to an inhibited sample performance in the platform. Future work will have to be conducted, not only to verify the findings of the initial experiments but also to improve the measurement platform and the theoretical model.
Rotary drums are tools used extensively in various prominent industries for their utility in heating and transporting particulate products. These processes are often inefficient and studies on heat transfer in rotary drums will reduce energy consumption as operating parameters are optimized. Research on this subject has been ongoing at ASU; however, the design of the rotary drum used in these studies is restrictive and experiments using radiation heat transfer have not been possible.<br/><br/>This study focuses on recounting the steps taken to upgrade the rotary drum setup and detailing the recommended procedure for experimental tests using radiant heat transfer upon completed construction of the new setup. To develop an improved rotary drum setup, flaws in the original design were analyzed and resolved. This process resulted in a redesigned drum heating system, an altered thinner drum, and a larger drum box. The recommended procedure for radiant heat transfer tests is focused on determining how particle size, drum fill level, and drum rotation rate impact the radiant heat transfer rate.
This paper explores to mitigate the issue of Formula SAE brakes vaporizing by creating a computational model to determine when the fluid may boil given a velocity profile and brake geometry. The paper explores various parameters and assumptions and how they may lead to error determining when the brake fluid will vaporize. Common assumptions such as a constant convection coefficient are questioned throughout the paper and compared to methods requiring higher computational power. Throughout this model, a significant dependence on the heat partition factor is found on the final steady state temperature of the brake fluid is found, and a sensitivity analysis is performed to determine the effect of its variation.
Thermophotovoltaic energy conversion is seen as a viable option for efficiently converting heat to electricity. There are three key components to a thermophotovoltaic (TPV) system: a heat source, a heat emitter and a photovoltaic (PV) cell. A heat source heats up the emitter which causes the emitter to release thermal radiation. The photons are absorbed by a PV cell when they are acting above the bandgap energy. The PV cell then generates electricity from this thermal radiation. In theory, efficiency of a TPV system can be well above 50%. In order for TPV to reach large-scale adaptation, an efficiency at or above 20% is needed. In this project, a high-temperature heater capable of reaching 1000K was developed. The heater involved a copper block machined to hold two cartridge heaters, as well as two thermocouples. It has an accompanying copper lid that can be screwed tight to the main block, with an emitter in between. There is an aperture to allow radiation through the casing towards the PV cell. Preliminary thermal analysis showed that the heater provides uniform temperature distribution across the emitter, which is necessary for proper radiation. A mounting system was also designed to implement the heater into the overall TPV system. Current work is being done to lower the radiation loss from the heater and mounting system, as well as implementation of all auxiliary components to begin testing. The maximum temperature of the heater, radiation heat flux received by the cell, and overall power output and efficiency of the system will be tested.
