Filtering by
- All Subjects: Algae
- Creators: Chemical Engineering Program
- Creators: Arizona State University. School of Sustainable Engineering and the Built Environment
This study analyzes the feasibility of using algae cultivated from wastewater effluent to produce a biodiesel feedstock. The goal was to determine if the energy produced was greater than the operational energy consumed without consideration to constructing the system as well as the emissions and economic value associated with the process.
Four scenarios were created:
1) high-lipid, dry extraction.
2) high-lipid, wet extraction.
3) low-lipid, dry extraction.
4) low-lipid, wet extraction.
In all cases, the system required more energy than it produced. In high lipid scenarios, the energy produced is close to the energy consumed, and a positive net energy balance may be achieved with minor improvements in technology or accounting for coproducts. In the low lipid scenarios, the energy balance is too negative to be considered feasible. Therefore the lipid content affects the decision to implement algae cultivation.
The dry extraction and the wet extraction both require some level of mechanical drying and this makes the two methods yield similar results in terms of the energy analysis. Therefore, the extraction method does not dramatically affect the decision for implementing algae-based oil production from an energetic standpoint. The economic value of the oil in both high lipid scenarios results in a net profit despite the negative net energy. Emission calculations resulted in avoiding a significant amount of CO2 for high lipid scenarios but not for the low lipid scenarios. The CO2 avoided does not account for non-lipid biomass, so this number is an underestimation of the final CO2 avoided from the end products.
While the term "CO2 avoided" has been used for this study, it should be noted that this CO2 would be emitted upon use as a fuel source. These emissions, however, are not “new” CO2 because it has already been emitted and is being captured and recycled. Currently, literature is very divisive on the lipid content present in algae and this study shows that lipid content has a tremendous affect on energy and emissions impacts. The type of algae that can grow in wastewater effluent also should be investigated as well as the conditions that promote high lipid accumulation. The dewatering phase must be improved as it is extremely energy intensive and dominates the operational energy balance.
In order to compete, wet extraction must have a much more significant effect on the drying phase and must avoid the use of the human toxicants methanol and chloroform. Additionally, while the construction phase was beyond the scope of this project it may be a critical aspect in determining the feasibility these systems. Future research in this field should focus on lipid production, optimizing the belt dryer or finding a different method of dewatering, and allocating the coproducts.
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
Temperature swing adsorption is a commonly used gas separation technique, and is being<br/>further researched as a method of carbon capture. Carbon capture is becoming increasingly<br/>important as a potential way to slow global warming. In this study, algae-derived activated<br/>carbon adsorbents were analyzed for their carbon dioxide adsorption effectiveness.<br/>Algae-derived carbon adsorbents were synthesized and then studied for their adsorption<br/>isotherms and adsorption breakthrough behavior. From the generated isotherm plots, it was<br/>determined that the carbonization temperature was not high enough and that more batches of<br/>adsorbent would have to be made to more accurately analyze the adsorptive potential of the<br/>algae-derived carbon adsorbent.