Matching Items (27)

Process Design and Refinement for Bioproduction of Sustainable Butanol

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This document outlines the research work done by Shona Becwar in the process design and refinement for the production of sustainable butanol from Clostridium, along with the required background knowledge

This document outlines the research work done by Shona Becwar in the process design and refinement for the production of sustainable butanol from Clostridium, along with the required background knowledge on the subject. The process that the microbiological organisms go through to produce butanol must be an oxygen free environment for up to 21 days with multiple perforations made into the environment in this period. There was not previously a cost effective method to do this, even in small scale. It was determined that using a butyl rubber septa would allow for the environment to be sustained during the growth process. The pervaporation process was losing butanol product at a rate of approximately 60%, changing the tubing from silicon to stainless steel allowed for a mere 7% loss during the separation process, greatly increasing the prospective of upscaling this process. These improvements to the sustainable butanol production process will allow for a more efficient, therefore more economically competitive product which can be used as a drop in equivalent to the current butanol market.

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  • 2016-05

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Determination of Higher Heating Value for Algal Products

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Hydrothermal Liquefaction of Algae represents one of many pathways for the sustainable replacement of fossil fuels in transportation. When processing and researching algal biofuel, determination of the higher heating value

Hydrothermal Liquefaction of Algae represents one of many pathways for the sustainable replacement of fossil fuels in transportation. When processing and researching algal biofuel, determination of the higher heating value (HHV) is paramount. Bomb calorimetry represents to current method for direct determination of HHV. When determining HHV’s indirectly, the industry standard is using one of many linear correlations relating elemental composition to HHV. Most of these correlations were developed from coal industry data, meaning that they do not necessarily fit algal product data well. In this study bomb calorimetry data and CHNS/O elemental composition data were collected for Chlorella, Micract, GS 5587.1, Kirchnella, and Gal 87.1 MM8 algae species. This data was added to CHNS/O and HHV values for other algal products in literature, and utilized to test the accuracy of the Dulong, Gumz, Vandralek and Boie correlations for algae products. Several preliminary algae specific correlations were proposed through a linear regression model of the data. Of the 5 samples tested, Kirchnella exhibited the highest HHV (23.2405 ± 0.0216 MJ/kg) and Chlorella exhibited the lowest (20.2055 ± 0.0484 MJ/kg). For both the experimental, and literature CHNS/O vs HHV data, the Vandralek and Boie correlations provided the best approximations in this study. For the totality of the data collected and researched in this study, 6 of 8 proposed correlations outperformed the Vandralek equation for HHV approximation. The most promising proposed correlations incorporated multiple linear regressions for elemental fractions of CHS, CHSO and CHNSO. Being that only 20 distinct algal product samples were regressed to create the proposed correlations, more data should be incorporated before publication of a final correlation. This study should serve as a starting point for the compilation of an exhaustive database for algal product assay and HHV data.

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  • 2017-05

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New insights into the pore development mechanism of layered hydroxides upon thermal activation

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Layered double hydroxides (LDHs), also known as hydrotalcite-like materials, are extensively used as precursors for the preparation of (photo-)catalysts, electrodes, magnetic materials, sorbents, etc. The synthesis typically involves the transformation

Layered double hydroxides (LDHs), also known as hydrotalcite-like materials, are extensively used as precursors for the preparation of (photo-)catalysts, electrodes, magnetic materials, sorbents, etc. The synthesis typically involves the transformation to the corresponding mixed metal oxide via calcination, resulting in atomically dispersed mixed metal oxides (MMOs). This process alters the porosity of the materials, with crucial implications for the performance in many applications. Yet, the mechanisms of pore formation and collapse are poorly understood. Combining an integrated in situ and ex situ characterization approach, here we follow the evolution of porosity changes during the thermal decomposition of LDHs integrating different divalent (Mg, Ni) and trivalent (Al, Ga) metals. Variations in porous properties determined by high-resolution argon sorption are linked to the morphological and compositional changes in the samples by in situ transmission electron microscopy coupled with energy dispersive X-ray spectroscopy, which is facilitated by the synthesis of well crystallized LDHs of large crystal size. The observations are correlated with the phase changes identified by X-ray diffraction, the mass losses evidenced by thermogravimetric analysis, the structural changes determined by infrared and nuclear magnetic resonance spectroscopy, and the pore connectivity analyzed by positron annihilation spectroscopy. The findings show that the multimetallic nature of the LDH governs the size and distribution (geometry, location, and connectivity) of the mesopores developed, which is controlled by the crystallization of the MMO phase, providing key insights for the improved design of porous mixed metal oxides.

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  • 2017-05

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Characterizing the activity of alcohol dehydrogenase from Lactobacillus brevis on primary and secondary alcohol biofuel precursors

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The R-specific alcohol dehydrogenase (RADH or LVIS_0347) from Lactobacillus brevis LB19 was found to possess activity on several short chain aldehydes and ketones. This broad substrate specificity was previously uncharacterized.

The R-specific alcohol dehydrogenase (RADH or LVIS_0347) from Lactobacillus brevis LB19 was found to possess activity on several short chain aldehydes and ketones. This broad substrate specificity was previously uncharacterized. To demonstrate its relevance to the biofuels industry as well as its broader utility for chiral reductions, a detailed characterization was performed to further investigate the activity and function of RADH.

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  • 2015-05

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

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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Simulations of Pressure Swing Adsorption of Methane - Carbon Dioxide System

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Separation of carbon dioxide and methane for the upgrade of natural gas through use of pressure swing adsorption could potentially save large amounts of energy from the current, costly process

Separation of carbon dioxide and methane for the upgrade of natural gas through use of pressure swing adsorption could potentially save large amounts of energy from the current, costly process of cryogenic distillation and provides greater cost effectiveness for carbon dioxide capture, and provide larger product flowrates than membrane permeation separation. The purpose of this study is to analyze the effects of varying initial conditions of a MatLab simulation, courtesy of Mai Xu, a graduate student at ASU, designed to use Langmuir isotherms, mass transfer equations, and adsorbent and gas properties to simulate a pressure swing adsorption process with a mixture of methane and carbon dioxide gas feed. The effects that will be varied are the adsorption/desorption time, pressurization/depressurization time, adsorption feed composition, desorption purge composition, adsorption pressure, desorption pressure, adsorption flow rate, and desorption flow rate. The study found that the trends in methane purity and production generally follow the trends predicted by literature and relevant equations, with pressure boundaries being the largest impacting factor. In addition there was a markedly inverse correlation between purity of methane product and the productivity of the system. This trend was only violated in one instance, at very low vacuum pressure during desorption, which could indicate an area that requires further study. Overall, the main areas of improvement in pressure swing adsorption for this system would be improving the selectivity of adsorption of carbon dioxide over methane, which requires improvement and change of the adsorbent, and more extreme vacuum pressures during desorption, both of which will increase methane yield and reduce operating costs.

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  • 2018-05

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Nanostructured Faujasite Zeolites for Carbon Dioxide Adsorption: Adsorption Equilibrium and Dynamics Modeling

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Carbon capture is an essential way to reduce greenhouse gas emissions. One way to decrease the emissions is through the use of adsorbents such as zeolites. Dr. Dong-Kyun Seo’s grou

Carbon capture is an essential way to reduce greenhouse gas emissions. One way to decrease the emissions is through the use of adsorbents such as zeolites. Dr. Dong-Kyun Seo’s group (School of Molecular Sciences, Arizona State University) synthesized the nanostructured faujasite (NaX). The zeolite was characterized using Scanning Electron Microscopy (SEM) and the physisorption properties were determined using ASAP 2020. ASAP 2020 tests of the nano-zeolite pellets at 77K in a liquid N2 bath determined the BET surface area of 547.1 m2/mol, T-plot micropore volume of 0.2257 cm3/g, and an adsorption average pore width of 5.9 Å. The adsorption isotherm (equilibrium) of CH4, N2, and CO2 were measured at 25ºC. Adsorption isotherm experiments concluded that the linear isotherm was the best fit for N2, and CH4 and the Sips isotherm was a better fit than the Langmuir and Freundlich isotherm for CO2. At 25ºC and 1 atm the zeolite capacity for CO2 is 4.3339 mmol/g, 0.1948 mmol/g for CH4, and 0.3534 mmol/g for N2. The zeolite has a higher CO2 capacity than the conventional NaX zeolite. Breakthrough experiments were performed in a fixed bed 22in, 0.5 in packing height and width at 1 atm and 298 K with nano-zeolite pellets. The gas chromatographer tested and recorded the data every two minutes with a flow rate of 10 cm3/min for N2 and 10 cm3/min CO2. Breakthrough simulations of the zeolite in a fixed bed adsorber column were conducted on MATLAB utilizing varying pressures, flow rates, and fed ratios of various CO2, N2 and CH4. Simulations using ideal adsorbed solution theory (IAST) calculations determined that the selectivity of CO2 in flue gas (15% CO2 + 85% N2) is 571.79 at 1 MPa, significantly higher than commercial zeolites and literature. The nanostructured faujasite zeolite appears to be a very promising adsorbent for CO2/N2 capture from flue gas and the separation of CO2/N2.

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  • 2018-05

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Can Biochar Be Converted into Activated Carbon?

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In Nepal, a viable solution for environmental management, food and water security is the production of biochar, a carbon material made of plants burned in low oxygen conditions. Currently, the

In Nepal, a viable solution for environmental management, food and water security is the production of biochar, a carbon material made of plants burned in low oxygen conditions. Currently, the biochar is manufactured into charcoal briquettes and sold on the market for energy usage, however this may not provide the best value for community members who make less than a dollar a day and sell the biochar for as little as 16 cents per kilogram. This thesis seeks to improve the price of biochar and help their livelihoods as well as explore innovative solutions. One way to improve biochar while addressing water security problems is to create activated carbon, which uses its heightened porosity to adsorb contaminants from water or air. Activated carbon is also worth 100x the price of biochar. This thesis evaluates the mass content of biochar produced in Nepal, comparing it to literature values, and performed gravimetric and thermogravimetric analysis, comparing it to Activated Charcoal. Analysis of the biochar system used in Nepal reveals that the byproduct of biochar, biofuels, is highly underutilized. The higher heating value of biochar is 17.95 MJ/kg, which is much lower than other charcoals which burn around 30 MJ/kg. Low volatile content, less than 5% in biochar, provides a smokeless briquette, which is favorable on the market, however low heating value and misutilizations of biofuels in the solution indicate that creating a briquette is not the best use for biochar. Ash content is really high in this biochar, averaging around 12% and it may be due to the feedstock, a composite between Mikania and Lantana, which have 5.23% and 10.77% ash content respectively. This does not necessarily indicate a poor quality biochar, since ash values can vary widely between charcoals. Producing activated charcoal from this biochar is a favored solution; it will increase the price of the biochar, provide water security solutions, and be an appropriate process for this biochar, where heating value and underutilization of biofuel byproducts pose a problem.

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  • 2019-05

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Production of Biofuel from Algae and Salicornia using Hydrothermal Liquefaction (HTL) Technique

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Fossil fuels have been the primary source of energy in the world for many decades. However, they are among the top contributors of the greenhouse gas emissions in the

Fossil fuels have been the primary source of energy in the world for many decades. However, they are among the top contributors of the greenhouse gas emissions in the atmosphere. The objective of this research was to produce a more environmentally friendly biofuel from Algae-Helix and Salicornia biomasses. Experiments were conducted using a hydrothermal liquefaction (HTL) technique in the HTL reactor to produce biofuel that can potentially replace fossil fuel usage. Hydrothermal Liquefaction is a method used to convert the biomass into the biofuels. HTL experiments on Algae-Helix and Salicornia at 200°C-350°C and 430psi were performed to investigate the effect of temperature on the biocrude yield of the respective biomass used. The effect of the biomass mixture (co-liquefaction) of Salicornia and algae on the amount of biocrude produced was also explored. The biocrude and biochar (by-product) obtained from the hydrothermal liquefaction process were also analyzed using thermogravimetric analyzer (TGA). The maximum biocrude yield for the algae-helix biomass and for the Salicornia biomass were both obtained at 300°C which were 34.63% and 7.65% respectively. The co-liquefaction of the two biomasses by 50:50 provided a maximum yield of 17.26% at 250°C. The co-liquefaction of different ratios explored at 250°C and 300°C concluded that Salicornia to algae-helix ratio of 20:80 produced the highest yields of 22.70% and 31.97%. These results showed that co-liquefaction of biomass if paired well with the optimizing temperature can produce a high biocrude yield. The TGA profiles investigated have shown that salicornia has higher levels of ash content in comparison with the algae-helix. It was then recommended that for a mixture of algae and Salicornia, large-scale biofuel production should be conducted at 250℃ in a 20:80 salicornia to algae biocrude ratio, since it lowers energy needs. The high biochar content left can be recycled to optimize biomass, and prevent wastage.

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  • 2019-05

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Production of Biofuel from Algae and Salicornia using Hydrothermal Liquefaction (HTL) Technique

Description

Fossil fuels have been the primary source of energy in the world for many decades. However, they are among the top contributors of the greenhouse gas emissions in the atmosphere.

Fossil fuels have been the primary source of energy in the world for many decades. However, they are among the top contributors of the greenhouse gas emissions in the atmosphere. The objective of this research was to produce a more environmentally friendly biofuel from Algae-Helix and Salicornia biomasses. Experiments were conducted using a hydrothermal liquefaction (HTL) technique in the HTL reactor to produce biofuel that can potentially replace fossil fuel usage. Hydrothermal Liquefaction is a method used to convert the biomass into the biofuels. HTL experiments on Algae-Helix and Salicornia at 200°C-350°C and 430psi were performed to investigate the effect of temperature on the biocrude yield of the respective biomass used. The effect of the biomass mixture (co-liquefaction) of Salicornia and algae on the amount of biocrude produced was also explored. The biocrude and biochar (by-product) obtained from the hydrothermal liquefaction process were also analyzed using thermogravimetric analyzer (TGA). The maximum biocrude yield for the algae-helix biomass and for the Salicornia biomass were both obtained at 300°C which were 34.63% and 7.65% respectively. The co-liquefaction of the two biomasses by 50:50 provided a maximum yield of 17.26% at 250°C. The co-liquefaction of different ratios explored at 250°C and 300°C concluded that Salicornia to algae-helix ratio of 20:80 produced the highest yields of 22.70% and 31.97%. These results showed that co-liquefaction of biomass if paired well with the optimizing temperature can produce a high biocrude yield. The TGA profiles investigated have shown that salicornia has higher levels of ash content in comparison with the algae-helix. It was then recommended that for a mixture of algae and Salicornia, large-scale biofuel production should be conducted at 250℃ in a 20:80 salicornia to algae biocrude ratio, since it lowers energy needs. The high biochar content left can be recycled to optimize biomass, and prevent wastage.

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  • 2019-05