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- All Subjects: chemical engineering
- Creators: Deng, Shuguang
- Creators: Green, Matthew D
In this thesis, a novel series of grafted siloxanes have been explored for their probable application in the healthcare industry. The siloxanes are grafted with poly(ethylene glycol) (PEG) and quaternary ammonium salt (QUAT). The effects of varying 1) molar ratios of QUAT to PEG and 2) PEG chain length on contact angle, surface tension, critical micelle concentration (CMC), and micelle assembly properties were studied. In contact angle experiments, the hydrophilicity of grafted siloxanes increased by grafting PEG and QUAT. The amphiphilicity increases and CMC decreases as the PEG chain length shortens. Adding QUAT also reduces CMC. These trends were observed in surface tension and Isothermal Titration Calorimetry experiments. A change in self-assembly behaviour was also observed in Dynamic Light Scattering experiments upon increasing the PEG chain length and its ratio relative to the quaternary ammonium in the siloxane polymer.
These polymers have also been studied for their probable application as a sensitive 1H NMR spectroscopy indicator of tissue oxygenation (pO2) based on spectroscopic spin-lattice relaxometry. The proton imaging of siloxanes to map tissue oxygenation levels (PISTOL) technique is used to map T1 of siloxane polymer, which is correlated to dynamic changes in tissue pO2 at various locations by a linear relationship between pO2 and 1/T1. The T1-weighted echo spin signals were observed in an initial study of siloxanes using the PISTOL technique.
The change in the ratio of QUAT to PEG and the varying chain length of PEG have a significant effect on the physical property characteristics of siloxane graft copolymers. The conclusions and observations of the present work serve as a benchmark study for further development of adaptive polymers and for the creation of integrated “nanoscale” probes for PISTOL oximetry and drug delivery.
Underreporting of energy intake (EI) has been found to be an important consideration that interferes with accurate weight control assessment and the effective use of energy balance (EB) models in an intervention setting. To better understand underreporting, a variety of estimation approaches are developed; these include back-calculating energy intake from a closed-form of the EB model, a Kalman-filter based algorithm for recursive estimation from randomly intermittent measurements in real time, and two semi-physical identification approaches that can parameterize the extent of systematic underreporting with global/local modeling techniques. Each approach is analyzed with intervention participant data and demonstrates potential of promoting the success of weight control.
In addition, substantial efforts have been devoted to develop participant-validated models and incorporate into the Hybrid Model Predictive Control (HMPC) framework for closed-loop interventions. System identification analyses from Phase I led to modifications of the measurement protocols for Phase II, from which longer and more informative data sets were collected. Participant-validated models obtained from Phase II data significantly increase predictive ability for individual behaviors and provide reliable open-loop dynamic information for HMPC implementation. The HMPC algorithm that assigns optimized dosages in response to participant real time intervention outcomes relies on a Mixed Logical Dynamical framework which can address the categorical nature of dosage components, and translates sequential decision rules and other clinical considerations into mixed-integer linear constraints. The performance of the HMPC decision algorithm was tested with participant-validated models, with the results indicating that HMPC is superior to "IF-THEN" decision rules.
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
quickly follows the initial transient flow regime in the constant-rate production of
a closed boundary hydrocarbon reservoir. The characterization of the PSS flow
regime is of importance in describing the reservoir pressure distribution as well as the
productivity index (PI) of the flow regime. The PI describes the production potential
of the well and is often used in fracture optimization and production-rate decline
analysis. In 2016, Chen determined the exact analytical solution for PSS flow of a
fully penetrated vertically fractured well with finite fracture conductivity for reservoirs
of elliptical shape. The present work aimed to expand Chen’s exact analytical solution
to commonly encountered reservoirs geometries including rectangular, rhomboid,
and triangular by introducing respective shape factors generated from extensive
computational modeling studies based on an identical drainage area assumption. The
aforementioned shape factors were generated and characterized as functions for use
in spreadsheet calculations as well as graphical format for simplistic in-field look-up
use. Demonstrative use of the shape factors for over 20 additional simulations showed
high fidelity of the shape factor to accurately predict (mean average percentage error
remained under 1.5 %) the true PSS constant by modulating Chen’s solution for
elliptical reservoirs. The methodology of the shape factor generation lays the ground
work for more extensive and specific shape factors to be generated for cases such as
non-concentric wells and other geometries not studied.
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UV, the samples were exposed to sunlight for up to 210 days and analyzed under Raman spectroscopy. Overall the physical and chemical changes with the polymers are evident and makes a way for the wastewater treatment plant to take necessary steps to capture the microplastics to avoid the release of any kind of degraded microplastics that could affect marine life and the environment.
Biochar from HTL of G. sulphuraria at 300 °C showed 15.98 and 5.27 % of phosphorous and nitrogen, respectively. HTL products from the biomass were analyzed for major elements through ICP-OES and CHNS/O. N and P are macronutrients that can be utilized in growing microalgae. This could reduce the operational demands in growing algae like, phosphorous mined to meet annual national demand for aviation fuel. Acidic leaching of these elements as phosphates and ammoniacal nitrogen was studied. Improved leaching of 49.49 % phosphorous and 95.71 % nitrogen was observed at 40 °C and pH 2.5 over a period of 7 days into the growth media. These conditions being ideal for growth of G. sulphuraria, leaching can be done in-situ to reduce overhead cost.
Growth potential of G. sulphuraria in leached media was compared to a standard cyanidium media produced from inorganic chemicals. Initial inhibition studies were done in the leached media at 40 °C and 2-3 vol. % CO2 to observe a positive growth rate of 0.273 g L-1 day-1. Further, growth was compared to standard media with similar composition in a 96 well plate 50 μL microplate assay for 5 days. The growth rates in both media were comparable. Additionally, growth was confirmed in a 240 times larger tubular reactor in a Tissue Culture Roller drum apparatus. A better growth was observed in the leached cyanidium media as compared to the standard variant.
Plastic consumption has reached astronomical amounts. The issue is the single-use plastics that continue to harm the environment, degrading into microplastics that find their way into our environment. Finding sustainable, reliable, and safe methods to break down plastics is a complex but valuable endeavor. This research aims to assess the viability of using biochar as a catalyst to break down polyethylene terephthalate (PET) plastics under hydrothermal liquefaction conditions. PET is most commonly found in single-use plastic water bottles. Using glycolysis as the reaction, biochar is added and assessed based on yield and time duration of the reaction. This research suggests that temperatures of 300℃ and relatively short experimental times were enough to see the complete conversion of PET through glycolysis. Further research is necessary to determine the effectiveness of biochar as a catalyst and the potential of process industrialization to begin reducing plastic overflow.