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- All Subjects: Climate Change
- All Subjects: Agriculture
- Creators: School of Sustainability
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
Is there a mismatch between urban farmers’ perceptions of their farm’s environmental sustainability and its actual environmental impact? Focusing on the use of water and nutrients on each farm as described by the farmers through interviews, it is evident that there is some level of disconnect between ideals and practices. This project may aid in bridging the gap between the two in regard to the farmers’ sustainability goals. This project will move forward by continuing interviews with farmers as well as collecting soil and water from the farms in order to more accurately quantify the sustainability of the farms’ practices. This project demonstrates that there is some degree of misalignment between perception and reality. Two farms claimed they were sustainable when their practices did not reflect that, while 2 farms said they were not sure if they were sustainable when their practices indicated otherwise. Samples from two farms showed high concentrations of nutrients and salts, supporting the idea that there may be a mismatch between perceived and actual sustainability.
To mitigate climate change, carbon needs to be removed from the atmosphere and stored for thousands of years. Currently, carbon removal and storage are voluntarily procured, and longevity of storage is inconsistently defined and regulated. Clauses can be added to procurement contracts to require long-term management and increase the durability of storage. Well-designed and properly enforced contracts can pave the way to future regulation for long-term carbon management.
As technology has evolved over time and the U.S. population increases each year, this thesis focuses on the ways in which food production has shifted from the original farm to table to industrialized, processed food systems. Through a rationalization perspective, this research looks to the history and repercussions of industrial agriculture as it has shifted over time. The term over-industrialization is used to operationalize the state of our current production methods. These methods focus extensively on the least expensive and most rapid methods to produce large yields of food products and pay no mind to ethics, respect of culture, land, or quality of products. Today, there is a shroud the corporations have placed over food production to ensure a “what we can’t see doesn’t affect us” belief system. In this way, the thesis provides insight on past, current, and future methods of manufacturing. I conclude that although plausible alternatives are present, continued research and substantial producer and consumer changes must be our main priority.
Climate change is impacting fisheries through ecological shifts altering the geographical distribution and quantity of fish species. About 60% of United States fish caught by volume is caught in the Alaska region, with Alaska's economy dependent on fisheries. Additionally, fisheries are an important source of employment for many Alaskan communities. Therefore, it is important to have policies and strategies in place to prepare for ongoing climate impacts. One step to support better tailoring policy to support those most likely to be negatively impacted is to identify the fishing communities most vulnerable to climate change. This study uses data on vulnerable fish species and fishery catch by species and community to identify what communities are most vulnerable to changing climate conditions. I identify 26 communities that are fishing climate vulnerable species. I then use vulnerable fish species revenue data to identify communities most at risk either because they generate a substantial amount of revenue from these species or a substantial proportion of their total revenue is derived from these species. Using species-specific revenue, I show that Sablefish contribute the most to this vulnerability.
This thesis will examine possible connection points between the health of a local environmental/climate news ecosystem and that local community’s belief in and vulnerability to the effects of climate change in Central Appalachia and Northern Virginia. The three counties that will be studied in Virginia are Arlington, Buchanan and Wise Counties. This research will be mainly a hypothesis-generating descriptive analysis of data, coupled with both interviews with researchers and local experts, in addition to observations from relevant literature about the possible connections between availability of environmental news with climate change, institutional belief and climate vulnerability data. The local history of resource extraction will also be explored. The point of this thesis is not to prove that a lack of access to strong, locally focused climate and environmental news increases vulnerability to the effects of climate change (although it does raise this as a possibility). Rather, it is to continue a conversation with journalists, media professionals and climate professionals about how to approach understanding and engaging groups left out of the climate conversation and groups who've been traditionally underserved by news media when it comes to climate information and appeals for institutional trust. This conversation is already happening, especially when it comes to the importance of the health of local, community focused news in general in Appalachia, but given the urgency and scale of the climate crisis, merits continuation and some inquiry into environmental news.