Filtering by
- All Subjects: conservation
- Creators: School of Sustainability
- 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
This 15-week long course is designed to introduce students, specifically in Arizona, to basic sustainability and conservation principles in the context of local reptile wildlife. Throughout the course, the students work on identifying the problem, creating visions for the desired future, and finally developing a strategy to help with reptile species survival in the valley. Research shows that animals in the classroom have led to improved academic success for students. Thus, through creating this course I was able to combine conservation and sustainability curriculum with real-life animals whose survival is directly being affected in the valley. My hope is that this course will help students identify a newfound passion and call to action to protect native wildlife. The more awareness and actionable knowledge which can be brought to students in Arizona about challenges to species survival the more likely we are to see a change in the future and a stronger sense of urgency for protecting wildlife. In order to accomplish these goals, the curriculum was developed to begin with basic concepts of species needs such as food and shelter and basic principles of sustainability. As the course progresses the students analyze current challenges reptile wildlife faces, like urban sprawl, and explore options to address these challenges. The course concludes with a pilot pitch where students present their solution projects to the school.
In 1996, a floral and faunal inventory of the southeastern slopes of the Marojejy Massif, which falls in a protected area known as the Parc national de Marojejy, was conducted in an ascending series of altitudinal transect zones. The 1996 research team worked in five altitudinal zones (referred to as transect zones). Between 3 October and 15 November 2021, a floral and faunal inventory was completed, replicating the locations surveyed in 1996 and closely the dates. Detected bird species were analyzed for changes in elevational distribution between 1996 and 2021. Birds were divided into three feeding behavior groups and tolerance to forest habitat degradation was considered.
Stakeholders impacted by oil development in the Section 1002 region include the Kaktovik community who lives within the Program Area, the Gwich’in people who live south of ANWR, the corporations who will be leasing the land, as well as the employees who will be working on the projects. These stakeholders share similar values and interests, however, when it comes down to the attainment of these values, there are significant differences in opinion. This debate comes down specifically to the desire to ensure stability for one’s family and community, as this means 2 different things to the majority stakeholders on this issue: The Inupiaq and the Gwich’in. The Inupiaq ,who live in Kaktovik specifically ,are particularly keen on the idea of drilling in the Section 1002 region, because the revenues and opportunities that come with the oil and gas development provide access to better standards of living and a more westernized way of life. The Gwich’in, however, value their relationship to the land and the caribou that are at risk of significant change. These 2 groups are critical to the debate, but the state and federal governments have the final say, and a financial incentive to move forward with the lease sales.
Utilizing the S-LCA framework, life cycle impacts of drilling on society are found using indicators that are identified and assessed using both qualitative and quantitative means. Although some conclusions are uncertain due to the forward-looking nature of this S-LCA, the Increasing/Decreasing trends can be identified and confidently attributed to the specific indicators.
Significant Results:
Significant issues this study has highlighted include the resulting impacts, both positive and negative, on the communities affected by oil and gas development in Section 1002. Significant stakeholders include the Kaktovik community, the Gwich’in people, the oil and gas workers in the state of Alaska, and the oil and gas companies themselves. The local residents are the most affected by the impacts of development, with significant issues pertaining to potential for significant lifestyle change, the increased risk of impact on subsistence species, the risks associated with pollution, and the effect on the economy through revenues and job availability.