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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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Nitrate and Selenate Microbial Reduction in the Membrane Biofilm Reactor for Artificial Mining Wastewater

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Nitrate (NO3- ) and selenate (SeO42-) are common contaminants found in mining wastewater. Biological treatment has proved successful using bacteria capable of respiring NO3- into nitrogen gas and SeO42- into Se°. The Membrane Biofilm Reactor (MBfR) utilizes biofilm communities

Nitrate (NO3- ) and selenate (SeO42-) are common contaminants found in mining wastewater. Biological treatment has proved successful using bacteria capable of respiring NO3- into nitrogen gas and SeO42- into Se°. The Membrane Biofilm Reactor (MBfR) utilizes biofilm communities on the surface of hollow-fiber membranes to transform oxidized water contaminants into innocuous reduced products. For this project, I set up two MBfRs in a lead and lag configuration to reduce NO3- [input at ~40-45 mg NO3-N/L] and SeO42- [0.62 mg/L], while avoiding sulfate (SO42-) [~1600-1660 mg/L] reduction. Over the course of three experimental phases, I controlled two operating conditions: the applied hydrogen pressure and the total electron acceptor loading. NO3- in the lead MBfR showed average reductions of 50%, 94%, and 91% for phases I, II, and III, respectively. In the lag MBfR, NO3- was reduced by 40%, 96%, and 100% for phases I, II, and III. NO2- was formed in Stage I when NO3- was not reduced completely; nevertheless NO2- accumulation was absent for the remainder of operation. In the lead MBfR, SeO42- was reduced by 65%, 87%, and 50% for phases I, II, and III. In the lag MBfR, SeO42- was reduced 60%, 27%, and 23% for phases I, II, and III. SO42- was not reduced in either MBfR. Biofilm communities were composed of denitrifying bacteria Rhodocyclales and Burkholderiales, Dechloromonas along with the well-known SeO42--reducing Thauera were abundant genera in the biofilm communities. Although SO42- reduction was suppressed, sulfate-reducing bacteria were present in the biofilm. To optimize competition for electron donor and space in the biofilm, optimal operational conditions were hydrogen pressures of 26 and 7 psig and total electron acceptor loading of 3.8 and 3.4 g H2/m2 day for the lead and lag MBfR, respectively.

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2016-05

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Characterizing Buffers to Maximize Peroxide Production in the Cathode Chamber of Microbial Fuel Cells

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Microbial fuel cells (MFCs) facilitate the conversion of organic matter to electrical current to make the total energy in black water treatment neutral or positive and produce hydrogen peroxide to assist the reuse of gray water. This research focuses on

Microbial fuel cells (MFCs) facilitate the conversion of organic matter to electrical current to make the total energy in black water treatment neutral or positive and produce hydrogen peroxide to assist the reuse of gray water. This research focuses on wastewater treatment at the U.S. military forward operating bases (FOBs). FOBs experience significant challenges with their wastewater treatment due to their isolation and dangers in transporting waste water and fresh water to and from the bases. Even though it is theoretically favorable to produce power in a MFC while treating black water, producing H2O2 is more useful and practical because it is a powerful cleaning agent that can reduce odor, disinfect, and aid in the treatment of gray water. Various acid forms of buffers were tested in the anode and cathode chamber to determine if the pH would lower in the cathode chamber while maintaining H2O2 efficiency, as well as to determine ion diffusion from the anode to the cathode via the membrane. For the catholyte experiments, phosphate and bicarbonate were tested as buffers while sodium chloride was the control. These experiments determined that the two buffers did not lower the pH. It was seen that the phosphate buffer reduced the H2O2 efficiency significantly while still staying at a high pH, while the bicarbonate buffer had the same efficiency as the NaCl control. For the anolyte experiments, it was shown that there was no diffusion of the buffers or MFC media across the membrane that would cause a decrease in the H2O2 production efficiency.

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2016-05

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Continuous Hydrogen Peroxide Production using Microbial Electrochemical Cells

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Alternative ion exchange membranes for implementation in a peroxide production microbial electrochemical cel (PP-MEC) are explored through membrane stability tests with NaCl electrolyte and stabilizer EDTA at varying operational pHs. PP-MEC performance parameters \u2014 H2O2 concentration, current density, coulombic efficiency

Alternative ion exchange membranes for implementation in a peroxide production microbial electrochemical cel (PP-MEC) are explored through membrane stability tests with NaCl electrolyte and stabilizer EDTA at varying operational pHs. PP-MEC performance parameters \u2014 H2O2 concentration, current density, coulombic efficiency and power input required \u2014 are optimized over a 7 month continuous operation period based on their response to changes in HRT, EDTA concentration, air flow rate and electrolyte. I found that EDTA was compatible for use with the membranes. I also determined that AMI membranes were preferable to CMI and FAA because it was consistently stable and maintained its structural integrity. Still, I suggest testing more membranes because the AMI degraded in continuous operation. The PP-MEC produced up to 0.38 wt% H2O2, enough to perform water treatment through the Fenton process and significantly greater than the 0.13 wt% batch PP-MEC tests by previous researchers. It ran at > 0.20 W-hr/g H2O2 power input, ~ three orders of magnitude less than what is required for the anthraquinone process. I recommend high HRT and EDTA concentration while running the PP- MEC to increase H2O2 concentration, but low HRT and low EDTA concentration to decrease power input required. I recommend NaCl electrolyte but suggest testing new electrolytes that may control pH without degrading H2O2. I determined that air flow rate has no effect on PP-MEC operation. These recommendations should optimize PP-MEC operation based on its application.

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2016-05

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A Sustainable Approach to Wastewater Treatment Using Microbial Fuel Cells with Peroxide Production

Description

Microbial fuel cells (MFCs) promote the sustainable conversion of organic matter in black water to electrical current, enabling the production of hydrogen peroxide (H2O2) while making waste water treatment energy neutral or positive. H2O2 is useful in remote locations such

Microbial fuel cells (MFCs) promote the sustainable conversion of organic matter in black water to electrical current, enabling the production of hydrogen peroxide (H2O2) while making waste water treatment energy neutral or positive. H2O2 is useful in remote locations such as U.S. military forward operating bases (FOBs) for on-site tertiary water treatment or as a medical disinfectant, among many other uses. Various carbon-based catalysts and binders for use at the cathode of a an MFC for H2O2 production are explored using linear sweep voltammetry (LSV) and rotating ring-disk electrode (RRDE) techniques. The oxygen reduction reaction (ORR) at the cathode has slow kinetics at conditions present in the MFC, making it important to find a catalyst type and loading which promote a 2e- (rather than 4e-) reaction to maximize H2O2 formation. Using LSV methods, I compared the cathodic overpotentials associated with graphite and Vulcan carbon catalysts as well as Nafion and AS-4 binders. Vulcan carbon catalyst with Nafion binder produced the lowest overpotentials of any binder/catalyst combinations. Additionally, I determined that pH control may be required at the cathode due to large potential losses caused by hydroxide (OH-) concentration gradients. Furthermore, RRDE tests indicate that Vulcan carbon catalyst with a Nafion binder has a higher H2O2 production efficiency at lower catalyst loadings, but the trade-off is a greater potential loss due to higher activation energy. Therefore, an intermediate catalyst loading of 0.5 mg/cm2 Vulcan carbon with Nafion binder is recommended for the final MFC design. The chosen catalyst, binder, and loading will maximize H2O2 production, optimize MFC performance, and minimize the need for additional energy input into the system.

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2015-05

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Narcotics Consumption Trends at a Southwestern U.S. University Campus in 2017-2018 Tracked By Wastewater-Based Epidemiology

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Current methods measuring the consumption of prescription and illicit drugs are often hampered by innate limitations, the data is slow and often restricted, which can impact the relevance and robustness of the associated data. Here, wastewater-based epidemiology (WBE) was applied

Current methods measuring the consumption of prescription and illicit drugs are often hampered by innate limitations, the data is slow and often restricted, which can impact the relevance and robustness of the associated data. Here, wastewater-based epidemiology (WBE) was applied as an alternative metric to measure trends in the consumption of twelve narcotics within a collegiate setting from January 2018 to May 2018 at a Southwestern U.S. university. The present follow-up study was designed to identify potential changes in the consumption patterns of prescription and illicit drugs as the academic year progressed. Samples were collected from two sites that capture nearly 100% of campus-generated wastewater. Seven consecutive 24-hour composite raw wastewater samples were collected each month (n = 68) from both locations. The study identified the average consumption of select narcotics, in units of mg/day/1000 persons in the following order: cocaine (528 ± 266), heroin (404 ± 315), methylphenidate (343 ± 396), amphetamine (308 ±105), ecstasy (MDMA; 114 ± 198), oxycodone (57 ± 28), methadone (58 ± 73), and codeine (84 ± 40). The consumption of oxycodone, methadone, heroin, and cocaine were identified as statistically lower in the Spring 2018 semester compared to the Fall 2017. Universities may need to increase drug education for the fall semester to lower the consumption of drugs in that semester. Data from this research encompasses both human health and the built environment by evaluating public health through collection of municipal wastewater, allowing public health officials rapid and robust narcotic consumption data while maintaining the anonymity of the students, faculty, and staff.

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2020-05