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Algal Fuels: A Future Less Green than the Plant

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The algal fuel industry has existed since the 1980s without fully commercializing a product. Algal fuels are potentially viable replacements for fossil fuels due to their fast cultivation, high oil content, carbon dioxide sequestration during growth, and ability to

The algal fuel industry has existed since the 1980s without fully commercializing a product. Algal fuels are potentially viable replacements for fossil fuels due to their fast cultivation, high oil content, carbon dioxide sequestration during growth, and ability to be grown on non-arable land. For this thesis, six companies from 61 investigated were interviewed about their history with biofuels, technological changes they have gone through, and views for the future of the industry. All companies interviewed have moved away from fuel production largely due to high production costs and have moved primarily toward pharmaceuticals and animal feed production as well as wastewater treatment. While most do not plan to return to the biofuel industry in the near future, a return would likely require additional legislation, increased technological innovation, and coproduction of multiple products.

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2019-05

Heterogeneous Catalysis for Organic Reactions

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This honors thesis is focused on two separate catalysis projects conducted under the mentorship of Dr. Javier Pérez-Ramírez at ETH Zürich. The first project explored ethylene oxychlorination over supported europium oxychloride catalysts. The second project investigated alkyne semihydrogenation over nickel

This honors thesis is focused on two separate catalysis projects conducted under the mentorship of Dr. Javier Pérez-Ramírez at ETH Zürich. The first project explored ethylene oxychlorination over supported europium oxychloride catalysts. The second project investigated alkyne semihydrogenation over nickel phosphide catalysts. This work is the subject of a publication of which I am a co-author, as cited below.

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

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2019-05

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Hydrothermal Liquefaction of Micro-Algae to Produce Liquid Biofuels

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Fossil fuels are currently the main source of energy in the world’s transportation sector. They are also the primary contributor to carbon emissions in the atmosphere, leading to adverse climate effects. The objective of the following research is to increase

Fossil fuels are currently the main source of energy in the world’s transportation sector. They are also the primary contributor to carbon emissions in the atmosphere, leading to adverse climate effects. The objective of the following research is to increase the yield and efficiency of algal biofuel in order to establish algal-derived fuel as a competitive alternative to predominantly used fossil fuels. Using biofuel commercially will reduce the cost of production and ultimately decrease additional carbon emissions. Experiments were performed using hydrothermal liquefaction (HTL) to determine which catalyst would enhance the algal biocrude oil and result in the highest quality biofuel product, as well as to find the optimal combination of processing temperature and manure co-liquefaction of biomass ratio. For the catalytic upgrading experiments, Micractenium Immerum algae was used in conjunction with pure H2, Pt/C, MO2C, and HZSM-5 catalysts at 350℃ and 400℃, 430 psi, and a 30-minute residence time to investigate the effects of catalyst choice and temperature on the crude oil yield. While all catalysts increased the carbon content of the crude oil, it was found that using HZSM-5 at 350℃ resulted in the greatest overall yield of about 75%. However, the Pt/C catalyst increased the HHV from 34.26 MJ/kg to 43.26 MJ/kg. Cyanidioschyzon merolae (CM) algae and swine manure were utilized in the co-liquefaction experiments, in ratios (algae to swine) of 80:20, 50:50, and 20:80 at temperatures of 300℃ and 330℃. It was found that a ratio of 80:20 at 330℃ produced the highest biocrude oil yield of 29.3%. Although the 80:20 experiments had the greatest biomass conversion and best supported the deacidification of the oil product, the biocrude oil had a HHV of 33.58 MJ/kg, the lowest between the three different ratios. However, all calorific values were relatively close to each other, suggesting that both catalytic upgrading and co-liquefaction can increase the efficiency and economic viability of algal biofuel.

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2020-05

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Electrochemical Characterization of a High-Current-Density Microbial Biocathode with an Air Diffusion Membrane

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In microbial fuel cells (MFCs) the biocathode is developed as a potential alternative to chemical cathodic catalysts, which are deemed as expensive and unsustainable for applications. These cells utilize different types of microorganisms as catalysts to promote biodegradation of organic

In microbial fuel cells (MFCs) the biocathode is developed as a potential alternative to chemical cathodic catalysts, which are deemed as expensive and unsustainable for applications. These cells utilize different types of microorganisms as catalysts to promote biodegradation of organic matter while simultaneously converting energy released in metabolic reactions into electrical energy. Most current research have focused more on the anodic microbes, including the current generating bacteria species, anodic microbial community composition, and the mechanisms of the extracellular electron transfer. Compared to the anode, research on the microbes of the biocathode of the MFCs are very limited and are heavily focused on the role of the bacteria in the system. Thus, further understand of the mechanism of the microbial community in the biocathode will create new engineering applications for sustainable energy. Previous research conducted by Strycharz-Glaven et al. presented an electrochemical analysis of a Marinobacter-dominated biocathode communitygrown on biocathodes in sediment/seawater-based MFCs. Chronoamperometry results indicated that current densities up to -0.04 A/m2 were produced for the biocathode. Cyclic voltammetry responses indicated a midpoint potential at 0.196 V ± 0.01 V. However, the reactor design for these experiments showed that no oxygen is supplied to the electrochemical system. By incorporating an air diffusion membrane to the cathode of the reactor, chronoamperometry results have produced current density in the system up to -0.15 A/m2. Cyclic voltammetry results have also displayed a midpoint potential of 0.25 V ± 0.01 V under scan rates of 0.2 mV/s. Thus, this electrochemical setup has increased the current output of the system.

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2016-05

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Squeezing Out Electricity: Computer-Aided Design and Optimization of Electrodes of Solid Oxide Fuel Cells

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Solid oxide fuel cells have become a promising candidate in the development of high-density clean energy sources for the rapidly increasing demands in energy and global sustainability. In order to understand more about solid oxide fuel cells, the important ste

Solid oxide fuel cells have become a promising candidate in the development of high-density clean energy sources for the rapidly increasing demands in energy and global sustainability. In order to understand more about solid oxide fuel cells, the important step is to understand how to model heterogeneous materials. Heterogeneous materials are abundant in nature and also created in various processes. The diverse properties exhibited by these materials result from their complex microstructures, which also make it hard to model the material. Microstructure modeling and reconstruction on a meso-scale level is needed in order to produce heterogeneous models without having to shave and image every slice of the physical material, which is a destructive and irreversible process. Yeong and Torquato [1] introduced a stochastic optimization technique that enables the generation of a model of the material with the use of correlation functions. Spatial correlation functions of each of the various phases within the heterogeneous structure are collected from a two-dimensional micrograph representing a slice of a solid oxide fuel cell through computational means. The assumption is that two-dimensional images contain key structural information representative of the associated full three-dimensional microstructure. The collected spatial correlation functions, a combination of one-point and two-point correlation functions are then outputted and are representative of the material. In the reconstruction process, the characteristic two-point correlation functions is then inputted through a series of computational modeling codes and software to generate a three-dimensional visual model that is statistically similar to that of the original two-dimensional micrograph. Furthermore, parameters of temperature cooling stages and number of pixel exchanges per temperature stage are utilized and altered accordingly to observe which parameters has a higher impact on the reconstruction results. Stochastic optimization techniques to produce three-dimensional visual models from two-dimensional micrographs are therefore a statistically reliable method to understanding heterogeneous materials.

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2016-05

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Nanomaterials for Thermally Safe Lithium-Ion Batteries

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The two central goals of this project were 1) to develop a testing method utilizing coatings on ultra-thin stainless steel to measure the thermal conductivity (k) of battery electrode materials and composites, and 2) to measure and compare the thermal

The two central goals of this project were 1) to develop a testing method utilizing coatings on ultra-thin stainless steel to measure the thermal conductivity (k) of battery electrode materials and composites, and 2) to measure and compare the thermal conductivities of lithium iron phosphate (LiFePO4, "LFP") in industry-standard graphite/LFP mixtures as well as graphene/LFP mixtures and a synthesized graphene/LFP nanocomposite. Graphene synthesis was attempted before purchasing graphene materials, and further exploration of graphene synthesis is recommended due to limitations in purchased product quality. While it was determined after extensive experimentation that the graphene/LFP nanocomposite could not be successfully synthesized according to current literature information, a mixed composite of graphene/LFP was successfully tested and found to have k = 0.23 W/m*K. This result provides a starting point for further thermal testing method development and k optimization in Li-ion battery electrode nanocomposites.

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2014-05

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Carbon Dioxide Separation by Ceramic-Carbonate Dual-Phase Membranes and Process Design for Membrane Reactor in IGCC Power Plant

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Currently, approximately 40% of the world’s electricity is generated from coal and coal power plants are one of the major sources of greenhouse gases accounting for a third of all CO2 emissions. The Integrated Gasification Combined Cycle (IGCC) has

Currently, approximately 40% of the world’s electricity is generated from coal and coal power plants are one of the major sources of greenhouse gases accounting for a third of all CO2 emissions. The Integrated Gasification Combined Cycle (IGCC) has been shown to provide an increase in plant efficiency compared to traditional coal-based power generation processes resulting in a reduction of greenhouse gas emissions. The goal of this project was to analyze the performance of a new SNDC ceramic-carbonate dual-phase membrane for CO2 separation. The chemical formula for the SNDC-carbonate membrane was Sm0.075Nd0.075Ce0.85O1.925. This project also focused on the use of this membrane for pre-combustion CO2 capture coupled with a water gas shift (WGS) reaction for a 1000 MW power plant. The addition of this membrane to the traditional IGCC process provides a purer H2 stream for combustion in the gas turbine and results in lower operating costs and increased efficiencies for the plant. At 900 °C the CO2 flux and permeance of the SNDC-carbonate membrane were 0.65 mL/cm2•min and 1.0×10-7 mol/m2•s•Pa, respectively. Detailed in this report are the following: background regarding CO2 separation membranes and IGCC power plants, SNDC tubular membrane preparation and characterization, IGCC with membrane reactor plant design, process heat and mass balance, and plant cost estimations.

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2014-05

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Synthesis and Characterization of Thin Supported PDMS/ZIF-71 Films for Pervaporative Biofuel Recovery

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The recovery of biofuels permits renewable alternatives to present day fossil fuels that cause devastating effects on the planet. Pervaporation is a separation process that shows promise for the separation of ethanol from biologically fermentation broths. The performance of thin

The recovery of biofuels permits renewable alternatives to present day fossil fuels that cause devastating effects on the planet. Pervaporation is a separation process that shows promise for the separation of ethanol from biologically fermentation broths. The performance of thin film composite membranes of polydimethylsiloxane (PDMS) and zeolite imidazolate frameworks (ZIF-71) dip coated onto a porous substrate are analyzed. Pervaporation performance factors of flux, separation factor and selectivity are measured for varying ZIF-71 loadings of pure PDMS, 5 wt%, 12.5 wt% and 25 wt% at 60 oC with a 2 wt% ethanol/water feed. The increase in ZIF-71 loadings increased the performance of PDMS to produce higher flux, higher separation factor and high selectivity than pure polymeric films.

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2014-05

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Computational Study of Ionic Liquids for Low Temperature MET Sensors

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Ionic liquids are salts with low melting temperatures that maintain their liquid form below 100 °C, or even at ambient temperature. Ionic liquids are conductive, electrochemically stable, non-volatile, and have a low vapor pressure, making them a class of excellent

Ionic liquids are salts with low melting temperatures that maintain their liquid form below 100 °C, or even at ambient temperature. Ionic liquids are conductive, electrochemically stable, non-volatile, and have a low vapor pressure, making them a class of excellent candidate materials for electrolytes in energy storage, electrodeposition, batteries, fuel cells, and supercapacitors. Due to their multiple advantages, the use of ionic liquids on Earth has been widely studied; however, further research must be done before their implementation in space. The extreme temperatures encountered during space travel and extra-terrestrial deployment have the potential to greatly affect the liquid electrolyte system. Examples of low temperature planetary bodies are the permanently shadowed sections of the moon or icy surfaces of Jupiter’s moons. Recent studies have explored the limits of glass transition temperatures for ionic liquid systems. The project is centered around the development of an ionic liquid system for a molecular electronic transducer seismometer that would be deployed on the low temperature system of Europa. For this project, molecular dynamics simulations used input intermolecular and intramolecular parameters that then simulated molecular interactions. Molecular dynamics simulations are based around the statistical mechanics of chemistry and help calculate equilibrium properties that are not easily calculated by hand. These simulations will give insight into what interactions are significant inside a ionic liquid solution. The simulations aim to create an understanding how ionic liquid electrolyte systems function at a molecular level. With this knowledge one can tune their system and its contents to adapt the systems properties to fit all environments the seismometers will experience.

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2020-05

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Synthesis and Characterization of 2D Metal-organic Frameworks for Mixed-matrix Membrane Gas Separations

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Membrane-based technology for gas separations is currently at an emerging stage of advancement and adoption for environmental and industrial applications due to its substantial advantages like lower energy and operating costs over the conventional gas separation technologies. Unfortunately, the available

Membrane-based technology for gas separations is currently at an emerging stage of advancement and adoption for environmental and industrial applications due to its substantial advantages like lower energy and operating costs over the conventional gas separation technologies. Unfortunately, the available polymeric (or organic) membranes suffer a trade-off between permeance and selectivity. Mixed matrix membranes (MMMs) containing two-dimensional (2D) metal-organic frameworks (MOFs) as fillers are a highly sought approach to redress this trade-off given their enhanced gas permeabilities and selectivities compared to the pure polymeric membrane. These MMMs are increasingly gaining attention by researchers due to their unique properties and wide small- and large-scale gas separation applications. However, straightforward and scalable methods for the synthesis of MOFs nanosheets have thus far been persistently elusive. This study reports the single-phase preparation, and characterization of MMMs with 2D MOFs nanosheets as fillers. The prepared MOF and the polymer matrix form the ‘dense’ MMMs which exhibit increased gas diffusion resistance, and thus improved separation abilities. The single-phase approach was more successful than the bi-phase at synthesizing the MOFs. The influence of sonication power and time on the characteristics and performance of the membranes are examined and discussed. Increasing the sonication power from 50% to 100% reduces the pore size. Additionally, the ultimate effect on the selectivity and permeance of the MMMs with different single gases is reported. Analysis of results with various gas mixers indicates further performance improvements in these MMMs could be achieved by increasing sonication time and tuning suitable membrane thicknesses. Reported results reveal that MMMs are excellent candidates for next-generation gas mixture separations, with potential applications in CO2 capture and storage, hydrogen recovery, alkene recovery from alkanes, and natural gas purification.

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2019-05