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- All Subjects: Renewable Energy
- Creators: Chemical Engineering Program
- Creators: Dooley, Kevin
- Status: Published
Although there have been many attempts to adapt EIP methodology to existing industrial sharing networks, most of them have failed for various factors: geographic restrictions by governmental organizations on use of technology, cost of technology, the inability of industries to effectively communicate their upstream and downstream resource usage, and to diminishing natural resources such as water, land and non-renewable energy (NRE) sources for energy production.
This paper presents a feasibility study conducted to evaluate the comparative environmental, economic, and geographic impacts arising from the use of renewable energy (RE) and NRE to power EIPs. Life Cycle Assessment (LCA) methodology, which is used in a variety of sectors to evaluate the environmental merits and demerits of different kinds of products and processes, was employed for comparison between these two energy production methods based on factors such as greenhouse gas emission, acidification potential, eutrophication potential, human toxicity potential, fresh water usage and land usage. To complement the environmental LCA analysis, levelized cost of electricity was used to evaluate the economic impact. This model was analyzed for two different geographic locations; United States and Europe, for 12 different energy production technologies.
The outcome of this study points out the environmental, economic and geographic superiority of one energy source over the other, including the total carbon dioxide equivalent emissions, which can then be related to the total number of carbon credits that can be earned or used to mitigate the overall carbon emission and move closer towards a net zero carbon footprint goal thus making the EIPs truly sustainable.
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 thesis explores the investigation of the project “Designing for a Post-Diesel Engine World”, a collaborative experiment between organizations within Arizona State University and an undisclosed company. This investigation includes the analysis of various renewable energy technologies and their potential to replace industrial diesel engines as used in the company’s business. In order to be competitive with diesel engines, the technology should match or exceed diesel in power output, have reduced environmental impact, and meet other criteria standards as determined by the company. The team defined the final selection criteria as: low environmental impact, high efficiency, high power, and high technology readiness level. I served as the lead Hydrogen Fuel Cell Researcher and originally hypothesized that PEM fuel cells would be the most viable solution. Results of the analysis led to PEM fuel cells and Li-ion batteries being top contenders, and the team developed a hybrid solution incorporating both of these technologies in a technical and strategic solution. The resulting solution design from this project has the potential to be modified and implemented in various industries and reduce overall anthropogenic emissions from industrial processes.